Composition containing 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

[Technical Field]

[0001] This disclosure relates to compositions containing fluororubber. [Background technology]

[0002] Patent Document 1 describes a method for producing a fluoropolymer, which includes the step of obtaining a fluoropolymer by polymerizing a fluoromonomer in an aqueous medium in the presence of a polymer (1) containing a polymerization unit (1) based on a monomer represented by the following general formula (1). CX2 = CY(-CZ2-O-Rf-A) (1) (In the formula, X is the same or different -H or -F, Y is -H, -F, alkyl group or fluorine-containing alkyl group, and Z is the same or different -H, -F, alkyl group or 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 having an ether bond. A is -COOM, -SO3M or -OSO3M (M is -H, a metal atom, -NR) 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (wherein X, Y, and Z are H or organic groups, at least one of them contains a fluorine atom.)

[0003] Patent Document 2 describes a method for producing a fluorine-containing copolymer, characterized in that, when separating the fluorine-containing copolymer by coagulation of an aqueous dispersion of the fluorine-containing copolymer produced by emulsion polymerization in the presence of ammonia water, a cationic surfactant and a water-soluble organic solvent are used as the coagulating agent. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2019 / 168183 [Patent Document 2] Japanese Unexamined Patent Publication No. 2004-285264 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0005] An object of the present disclosure is to provide a composition containing a polymer containing a specific polymerization unit and a fluororubber, wherein the content of the polymer containing the specific polymerization unit is significantly reduced. MEANS FOR SOLVING THE PROBLEMS

[0006] According to a first aspect of the present disclosure, there is provided a composition containing a polymer (I) containing a polymerization unit (I) based on a monomer (I) represented by the general formula (I) and a fluororubber, wherein the content of the polymer (I) is 0.0001 to 1.0% by mass relative to the fluororubber. 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 CF₃; 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.) EFFECTS OF THE INVENTION

[0007] According to the present disclosure, it is possible to provide a composition containing a polymer containing a specific polymerization unit and a fluororubber, wherein the content of the polymer containing the specific polymerization unit is significantly reduced. MODE FOR CARRYING OUT THE INVENTION

[0008] Before describing this disclosure in detail, we define or explain some of the terms used in this disclosure.

[0009] In this disclosure, fluororubber refers to an amorphous fluoropolymer. "Amorphous" means that the magnitude of the melting peak (ΔH) observed 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 by crosslinking. Elastomer 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 this disclosure, partially fluorinated rubber is a fluoropolymer containing fluoromonomer units, having a perfluoromonomer unit content of less than 90 mol% relative to total polymer units, having a glass transition temperature of 20°C or lower, and having a melting peak (ΔH) magnitude of 4.5 J / g or lower.

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

[0012] In this disclosure, a perfluoromonomer is a monomer that does not contain carbon-hydrogen atom bonds in its molecule. The perfluoromonomer may be a monomer in which some of the fluorine atoms bonded to the carbon atoms are replaced with chlorine atoms, or it may have nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, boron atoms, or silicon atoms in addition to carbon atoms. Preferably, the perfluoromonomer is a monomer in which all hydrogen atoms are replaced with fluorine atoms. The perfluoromonomer does not contain monomers that provide crosslinking sites.

[0013] A monomer that provides crosslinking sites is a monomer (curing site monomer) that has crosslinkable groups that provide crosslinking sites to a fluoropolymer for crosslinking by a curing agent.

[0014] In this 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 this disclosure, "organic group" means a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound. Examples of such "organic groups" are: Alkyl molecules 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-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO2-, and RaNRbSO2- (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, Rb is independently H or an alkyl group which may have one or more substituents) are included. As the above organic group, an alkyl group which may have one or more substituents is preferable.

[0016] Furthermore, in this disclosure, “substituent” means a substituteable group. Examples of such “substituent” are aliphatic group, aromatic group, heterocyclic group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino This includes 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, hydroxyl groups, cyano groups, sulfo groups, carboxyl 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 above aliphatic group may be saturated or unsaturated, and may also include a hydroxyl group, aliphatic oxy group, carbamoyl group, aliphatic oxycarbonyl group, aliphatic thio group, amino group, aliphatic amino group, acylamino group, carbamoylamino group, etc. Examples of the above aliphatic group include alkyl groups having a total of 1 to 8 carbon atoms, preferably 1 to 4, such as a methyl group, ethyl group, vinyl group, cyclohexyl group, carbamoylmethyl group, etc.

[0018] The above 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, and the like. Examples of the above aromatic group include aryl groups having 6 to 12 carbon atoms, preferably 6 to 10 total carbon atoms, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, and a 4-methanesulfonylphenyl group.

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

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

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

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

[0023] The above carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the above 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 above aliphatic sulfonyl group may be saturated or unsaturated, and may also have a hydroxyl group, aromatic group, aliphatic oxy group, carbamoyl group, aliphatic oxycarbonyl group, aliphatic thio group, amino group, aliphatic amino group, acylamino group, carbamoylamino group, etc. Examples of the above aliphatic sulfonyl group include alkyl sulfonyl groups having a total of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as a methanesulfonyl group.

[0025] The above aromatic sulfonyl group may have a hydroxyl group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, and the like. Examples of the above aromatic sulfonyl group include aryl sulfonyl groups with a total of 6 to 10 carbon atoms, such as a benzenesulfonyl group.

[0026] The above amino group may also have an aliphatic group, an aromatic group, a heterocyclic group, etc.

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

[0028] The aforementioned aliphatic sulfonamido group, aromatic sulfonamido group, and heterocyclic sulfonamido group may each be, for example, a methanesulfonamido group, a benzenesulfonamido group, a 2-pyridinesulfonamido group, or the like.

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

[0030] The aforementioned 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, or the like. Examples of the aforementioned aliphatic oxy group include alkoxy groups having a total carbon number of 1 to 8, preferably 1 to 6, such as a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, and a methoxyethoxy group.

[0031] The above 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, an aliphatic oxycarbonyl group, preferably an aliphatic group having 1 to 4 total carbon atoms, an aliphatic oxy group having 1 to 4 total carbon atoms, a halogen atom, a carbamoyl group having 1 to 4 total carbon atoms, a nitro group, or an aliphatic oxycarbonyl group having 2 to 4 total carbon atoms.

[0032] The above aliphatic thio group may be saturated or unsaturated, and more preferably an alkyl thio group having a total of 1 to 8 carbon atoms, or more preferably 1 to 6 carbon atoms, such as a methyl thio group, an ethyl thio group, a carbamoyl methyl thio group, or a t-butyl thio group.

[0033] The above-mentioned carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. Examples of the above-mentioned 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, 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. For example, the above-mentioned carbamoylamino group, methylcarbamoylamino group, N,N-dimethylcarbamoylamino group, phenylcarbamoylamino group, 4-pyridinecarbamoylamino group, etc.

[0034] In this disclosure, the ranges represented by endpoints include all numerical values ​​that fall within that range (for example, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

[0035] In this disclosure, the phrase "at least 1" includes all numbers greater than or equal to 1 (for example, 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] The following describes specific embodiments of this disclosure in detail, but this disclosure is not limited to the embodiments described below.

[0037] (composition) The compositions of this disclosure contain a polymer (I) and a fluororubber, which contain polymerization units (I) based on a monomer (I) represented by general formula (I). CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) (In the formula, X 1 and X 3 These are, independently, F, Cl, H, or CF3; X 2 is H, F, alkyl group or fluorine-containing alkyl group; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 Each of these is independently H, F, an alkyl group, or a fluorinated alkyl group; m is an integer of 1 or more.

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

[0039] The composition of this disclosure contains polymer (I) and fluororubber, and further, the content of polymer (I) is 0.0001 to 1.0% by mass relative to the fluororubber. As such, the composition of this disclosure has a significantly reduced polymer (I) content, so when crosslinking the composition of this disclosure, the crosslinking reaction proceeds smoothly, and the resulting crosslinked product has the excellent physical properties of fluororubber. For example, by using a composition with a significantly reduced polymer (I) content, 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 relative to the fluororubber, preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, preferably 0.5% by mass or less, and more preferably 0.2% by mass or less. 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 or fusion NMR. If polymer (I) contains carbonyl groups, it can also be determined by Fourier transform infrared spectroscopy. Also, see International Publication Nos. 2014 / 099453, 2010 / 075497, 2010 / 075496, 2011 / 008381, 2009 / 055521, 1987 / 007619, Japanese Patent Publication No. 61-293476, 2010 / 075494, 2010 / 075359, 2012 / 082454, 2006 / 119224, 2013 / 085864, International The measurement methods for each polymer are described in publications such as Publication No. 2012 / 082707, International Publication No. 2012 / 082703, International Publication No. 2012 / 082451, International Publication No. 2006 / 135825, International Publication No. 2004 / 067588, International Publication No. 2009 / 068528, Japanese Patent Publication No. 2004-075978, Japanese Patent Publication No. 2001-226436, International Publication No. 1992 / 017635, International Publication No. 2014 / 069165, and Japanese Patent Publication No. Hei 11-181009. The measurement methods for each polymer described in these publications can be used as methods for measuring the content of polymer (I).

[0042] The compositions disclosed herein can be produced by polymerizing a fluoromonomer in an aqueous medium in the presence of polymer (I) to obtain a polymerization dispersion containing fluororubber, and then performing one of the following treatments on the obtained polymerization dispersion. (1) The fluororubber in the polymerization dispersion is brought into contact with an alcohol having 3 to 6 carbon atoms per OH group to cause the fluororubber to coagulate. (2) The polymerization dispersion is frozen to cause the fluororubber to coagulate. (3) The fluororubber in the polymerization dispersion is brought into contact with a very limited type of organic solvent to cause the fluororubber to coagulate.

[0043] The polymer (I) content in the polymerization dispersion is preferably more than 0.20% by mass, more preferably more than 1.0% by mass, 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, relative to the fluororubber.

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

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

[0046] (Polymer (I)) The polymer (I) contained in the composition of this disclosure contains polymerization units (I) based on monomer (I) represented by general formula (I). CX 1 X 3 =CX 2 R(-CZ 1 Z 2 -A 0 ) m (I) (In the formula, X 1 and X 3 These are, independently, F, Cl, H, or CF3; X 2 is H, F, alkyl group or fluorine-containing alkyl group; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 Each of these is independently H, F, an alkyl group, or a fluorinated alkyl group; m is an integer of 1 or more.

[0047] In this disclosure, the anionic group includes not only anionic groups such as sulfate groups and carboxylate groups, but also functional groups that give anionic groups such as acidic groups like -COOH and acid-base groups like -COONH4. Anionic groups include sulfate groups, carboxylate groups, phosphate groups, phosphonate groups, sulfonate groups, or -C(CF3)2OM (wherein M is -H, a metal atom, -NR). 74. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (where is H or an organic group.) is preferred.

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

[0049] R is a linking group. In this disclosure, “linking group” is an (m+1) valence linking group, and if m is 1, it is a divalence linking group. The linking group may be a single bond, 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 for example, it may be 100 or less, or 50 or less.

[0050] The linking group may be linear or branched, cyclic or acyclic, 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 esters, amides, sulfonamides, carbonyls, carbonates, urethanes, ureas, and carbamates. The above linking group may not contain carbon atoms and may contain catenary heteroatoms such as oxygen, sulfur, or nitrogen.

[0051] m is an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1. If m is an integer greater than or equal to 2, then Z 1 , Z 2 and A 0 They may be the same or different. Next, we will describe a preferred configuration when m is 1 in general formula (I).

[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, the hydrogen atom bonded to the carbon atom may be replaced by a halogen other than fluorine, such as chlorine, and may or may not contain a double bond. Furthermore, R may be linear or branched, and may be cyclic or acyclic. In addition, R may contain a functional group (for example, an 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 a carbon atom, a hydrocarbon group in which some of the hydrogen atoms bonded to a carbon atom are replaced by fluorine atoms, or a hydrocarbon group in which all of the hydrogen atoms bonded to a carbon atom are replaced by fluorine atoms. These may contain oxygen atoms, double bonds, or functional groups.

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

[0057] R is preferably -(CH2) a -,-(CF2) a -,-(CF2) a -O-, -O-(CF2) a -,-(CF2) a -O-(CF2) b -, -O(CF2) a -O-(CF2) b -,-(CF2) a -[O-(CF2) b ] c -, -O(CF2) a-[O-(CF2) b ] c -,-[(CF2) a -O] b -[(CF2) c -O] d -, -O[(CF2) a -O] b -, -O[(CF2) a -O] b -[(CF2) c -O] d -,-O-[CF2CF(CF3)O] a -(CF2) b -, -O-(CF2) a -O-[CF(CF3)CF2O] b -,-O-[CF2CF(CF3)O] a -(CF2) b -O-, -O-[CF2CF(CF3)O] a -(CF2) b -O-[CF(CF3)CF2O] c -,-[CF2CF(CF3)O] a -,-[CF(CF3)CF2O] a -,-(CF2) a -O-[CF(CF3)CF2O] a -,-(CF2) a -O-[CF(CF3)CF2O] a -(CF2) b -,-[CF2CF(CF3)] a -CO-(CF2) b -, and at least one of these combinations. 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 for a, b, c, and d is, for example, 100.

[0058] R is more preferably at least one selected from -O-CF2-, -O-CF2CF2-, -O-CF2CF2-O-, -O-CF2CF2CF2-, -O-CF2CF2CF2-O-, -O-CF2CF(CF3)-O-, -O-CF2CF2-O-CF(CF3)CF2-O-, -O-CF2CF(CF3)-O-CF2CF2-O-, and -O-CF2CF(CF3)-O-CF2-.

[0059] As R, the general formula (r1): -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g - (r1) (wherein, each X 6 is independently H, F or CF3, e is an integer of 0 to 3, f is an integer of 0 to 3, and g is 0 or 1) is preferably a divalent group represented by the formula, and the general formula (r2): -CF2-O-(CX 7 2) e -(O) g - (r2) (wherein, each X 7 is independently H, F or CF3, e is an integer of 0 to 3, and g is 0 or 1) is more preferably a divalent group represented by the formula.

[0060] Specific examples suitable for R include -CF2-O-, -CF2-O-CF2-, -CF2-O-CH2-, -CF2-O-CH2CF2-, -O-CF2-, -O-CF2CF 2-, -O-CF2CF2CF2-, -O-CF2CF2CF2CF2-, -O-CF2CF(CF3)-O-CF2-, -O-CF2CF(CF3)-O-CF2CF2- , -CF2-O-CF2CF2-, -CF2-O-CF2CH2-, -CF2-O-CF2CF2CH2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3 )CF2-, -CF2-O-CF(CF3)CF2-O-, -CF2-O-CF(CF3)CF2-O-CF2-, -CF2-O-CF(CF3)CH2-, and the like. In particular, R is preferably a perfluoroalkylene group which may contain an oxygen atom, specifically -CF2-O-, -CF2-O-CF2-, -O-CF2-, -O-CF2CF2-, -O-CF2CF(CF3)-O-CF2-, -O-CF2CF(CF3)-O-CF2CF2-, -CF2-O-CF2CF2-, -CF2-O-CF(CF3)-, -CF2-O-CF(CF3)CF2-, or -CF2-O-CF(CF3)CF2-O-.

[0061] General formula (I) -R-CZ 1 Z 2 -For example, the general formula (s1): -CF2-O-(CX 6 2) e -{O-CF(CF3)} f -(O) g -CZ 1 Z 2 - (s1) (In the formula, X 6 Each of these is independently H, F, or CF3, e is an integer from 0 to 3, f is an integer from 0 to 3, g is 0 or 1, Z 1 and Z 2 Preferably, each of these is independently represented as H, F, an alkyl group, or a fluorine-containing alkyl group, and in formula (s1), Z 1 and Z 2 F or CF3 is more preferable, and it is even more preferable that one is F and the other is CF3.

[0062] Furthermore, in general formula (I), -R-CZ 1 Z 2 -For example, the general formula (s2): -CF2-O-(CX 7 2) e -(O) g -CZ 1 Z 2 - (s2) (In the formula, X 7 Each of them is independently H, F, or CF3, e is an integer from 0 to 3, g is 0 or 1, and Z 1 and Z 2 Preferably, each of these is independently represented as H, F, an alkyl group, or a fluorine-containing alkyl group, and in formula (s2), Z 1 and Z 2 F or CF3 is more preferable, and it is even more preferable that one is F and the other is CF3.

[0063] General formula (I) -R-CZ 1 Z 2- as -CF2-O-CF2-, -O-CF2CF2-, -O-CF2CF2CF2-, -O-CF2CF2CF2CF2-, -O-CF2CF(CF3)-O-CF2-, -O-CF2CF(CF3)-O-CF 2CF2-, -O-CF2CF(CF3)-O-CF2CF2CF2-, -CF2-O-CF(CF3)-, -CF2-OC(CF3)2-, -CF2-O-CF2-CF2-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2-C(CF3)2-, -CF2-O-CF2CF2-CF2-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF2CF2-C(CF3)2-, -CF2-O-CF(CF3)- CF2-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)-C(CF3)2-, -CF2-O-CF(CF3)CF2-CF2-, -CF2-O-CF(CF3)CF2-CF(CF3 )-, -CF2-O-CF(CF3)CF2-C(CF3)2-, -CF2-O-CF(CF3)CF2-O-CF2-, -CF2-O-CF(CF3)CF2-O-CF(CF3)-, or -CF2-O-CF(CF 3) CF2-OC(CF3)2- is preferred, -O-CF2CF2-, -O-CF2CF2CF2-, -O-CF2CF2CF2CF2-, -O-CF2CF(CF3)-O-CF2-, -O-CF2CF(CF3)-O- CF2CF2-, -CF2-O-CF(CF3)-, -CF2-O-CF2-CF(CF3)-, -CF2-O-CF2CF2-CF(CF3)-, -CF2-O-CF(CF3)-CF(CF3)-, -CF2-O-CF(CF3)CF2-CF(CF3)-, or -CF2-O-CF(CF3)CF2-O-CF(CF3)- are more preferred, and -O-CF2CF2-, -O-CF2CF(CF3)-O-CF2CF2- are even more preferred.

[0064] Polymer (I) is also preferably highly fluorinated. For example, anionic groups such as a phosphate group moiety (e.g., CH2OP(O)(OM)2) and a sulfate group moiety (e.g., CH2OS(O)2OM) (A 0Except for the above, it is preferable that 80% or more, 90% or more, 95% or more, or 100% of the CH bonds in polymer (I) are replaced with CF bonds.

[0065] Monomer (I) and polymer (I) have an anionic group (A 0 Except for ), it is also preferable that it has CF bonds and does not have CH bonds. That is, in general formula (I), X 1 , X 2 , and X 3 Preferably, all of the elements are F, and R is a perfluoroalkylene group having 1 or more carbon atoms. The perfluoroalkylene group may be linear or branched, 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 4 to 18.

[0066] The monomer (I) and polymer (I) may be partially fluorinated. That is, the monomer (I) and polymer (I) may have an anionic group (A 0 Except for the above, it is also preferable to have 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) may be -SO2M, -SO3M, -OSO3M, -COOM, -SO2NR'CH2COOM, -CH2OP(O)(OM)2, [-CH2O]2P(O)(OM), -CH2CH2OP(O)(OM)2, [-CH2CH2O]2P(O)(OM), -CH2CH2OSO3M, -P(O)(OM)2, -SO2NR'CH2CH2OP(O)(OM)2, [-SO2NR'CH2CH2O]2P(O)(OM), -CH2OSO3M, -SO2NR'CH2CH2OSO3M, or -C(CF3)2OM. Among these, -SO3M, -OSO3M, -COOM, -P(O)(OM)2 or -C(CF3)2OM are preferred, -COOM, -SO3M, -OSO3M, -P(O)(OM)2 or -C(CF3)2OM are more preferred, -SO3M, -COOM or -P(O)(OM)2 are even more preferred, and -SO3M or -COOM are particularly preferred.

[0068] M is H, a metal atom, NR 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 is either H or an organic group.

[0069] Examples of metal atoms include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred.

[0070] For M, this could be -H, a metal atom, or NR. 7 4 is preferred, and -H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR 7 4 is more preferred, -H, -Na, -K, -Li or NH4 is even more preferred, -H, -Na, -K or NH4 is even more preferred, -H, -Na or NH4 is particularly preferred, and -H or NH4 is most preferred.

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

[0072] The monomer (I) is also preferably the monomer represented by general formula (Ia). It is also preferable that polymer (I) is a polymer that contains polymerization units (Ia) based on monomers represented by general formula (Ia). CF2 = CF - O - Rf 0 -A 0 (Ia) (In the formula, A 0 Rf is an anionic group, 0 This is a perfluorinated divalent linking group that is perfluorinated and may be linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, and optionally contains one or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen.

[0073] The monomer (I) is also preferably the monomer represented by general formula (Ib). The polymer (I) is also preferably a polymer that contains polymerization units (Ib) based on monomers represented by general formula (Ib). CH2=CH-O-Rf 0 -A 0 (Ib) (In the formula, A 0 Rf is an anionic group, 0 (This is a perfluorinated divalent linking group defined by formula Ia.)

[0074] In general formula (I), A 0 A is a sulfate group, which is one preferred form. 0 For example, -CH2OSO3M, -CH2CH2OSO3M, or -SO2NR'CH2CH2OSO3M, where R' is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0075] A 0When is a sulfate group, examples of monomers represented by general formula (I) include CF2=CF(OCF2CF2CH2OSO3M), CF2=CF(O(CF2)4CH2OSO3M), CF2=CF(OCF2CF(CF3)CH2OSO3M), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OSO3M), CH2=CH(O(CF2)4CH2OSO3M), CF2=CF(OCF2CF2SO2N(CH3)CH2CH2OSO3M), CH2=CH(OCF2CF2CH2OSO3M), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OSO3M), CH2=CH(OCF2CF2CF2CH2OSO3M), etc. In the above formula, M is the same as above.

[0076] In general formula (I), A 0 A sulfonate group is also a preferred form. 0 For example, this is -SO3M, where M is the same as above.

[0077] A 0 When is a sulfonate group, examples of monomers represented by general formula (I) include CF2=CF(OCF2CF2SO3M), CF2=CF(O(CF2)3SO3M), CF2=CF(O(CF2)4SO3M), CF2=CF(OCF2CF(CF3)SO3M), CF2=CF(OCF2CF(CF3)OCF2CF2SO3M), CH2=CH(OCF2CF2SO3M), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO3M), CH2=CH(O(CF2)4SO3M), CH2=CH(O(CF2)3SO3M), etc. In the above formula, M is the same as above.

[0078] In general formula (I), A 0 A carboxylate group is also a preferred form. 0 For example, COOM or SO2NR'CH2COOM, where R' is H or an alkyl group having 1 to 4 carbon atoms, and M is the same as above. 0When is a carboxylate group, the monomers represented by general formula (I) are CF2=CF(OCF2CF2COOM), CF2=CF(O(CF2)3COOM), CF2=CF(O(CF2)4COOM), CF2=CF(O(CF2)5COOM), CF2=CF(OCF2CF(CF3)COOM), and CF2=CF(OCF2CF(CF3)O(CF2) n Examples include COOM) (where n is greater than 1), CH2=CH(OCF2CF2COOM), CH2=CH(O(CF2)4COOM), CH2=CH(O(CF2)3COOM), CF2=CF(OCF2CF2SO2NR'CH2COOM), CF2=CF(O(CF2)4SO2NR'CH2COOM), CF2=CF(OCF2CF(CF3)SO2NR'CH2COOM), CF2=CF(OCF2CF(CF3)OCF2CF2SO2NR'CH2COOM), CH2=CH(OCF2CF2SO2NR'CH2COOM), CF2=CF(OCF2CF(CF3)OCF2CF2CF2CF2SO2NR'CH2COOM), CH2=CH(O(CF2)4SO2NR'CH2COOM), CH2=CH(O(CF2)3SO2NR'CH2COOM), etc. 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 A phosphate group is also a preferred form. 0 Examples include -CH2OP(O)(OM)2, [-CH2O]2P(O)(OM), -CH2CH2OP(O)(OM)2, [-CH2CH2O]2P(O)(OM), [-SO2NR'CH2CH2O]2P(O)(OM), or SO2NR'CH2CH2OP(O)(OM)2, where R' is an alkyl group having 1 to 4 carbon atoms, and M is the same as above.

[0080] A 0When is a phosphate, the monomers represented by general formula (I) are CF2=CF(OCF2CF2CH2OP(O)(OM)2), CF2=CF(O(CF2)4CH2OP(O)(OM)2), CF2=CF(OCF2CF(CF3)CH2OP(O)(OM)2), CF2=CF(OCF2CF(CF3)OCF2CF2CH2OP(O)(OM)2), CF2=CF(OC Examples include F2CF2SO2N(CH3)CH2CH2OP(O)(OM)2), CF2=CF(OCF2CF2CF2CF2SO2N(CH3)CH2CH2OP(O)(OM)2), CH2=CH(OCF2CF2CH2OP(O)(OM)2), CH2=CH(O(CF2)4CH2OP(O)(OM)2), CH2=CH(O(CF2)3CH2OP(O)(OM)2), etc. In the above formulas, M is the same as above.

[0081] In general formula (I), A 0 A phosphonate group is also a preferred form. 0 When is a phosphonate group, the monomers represented by general formula (I) include CF2=CF(OCF2CF2P(O)(OM)2), CF2=CF(O(CF2)4P(O)(OM)2), CF2=CF(OCF2CF(CF3)P(O)(OM)2), CF2=CF(OCF2CF(CF3)OCF2CF2P(O)(OM)2), CH2=CH(OCF2CF2P(O)(OM)2), CH2=CH(O(CF2)4P(O)(OM)2), and CH2=CH(O(CF2)3P(O)(OM)2), where M is the same as above.

[0082] The monomer (I) is preferably monomer (1) represented by general formula (1). The polymer (I) is preferably a polymer (1) that includes polymerization units (1) based on monomers represented by general formula (1). CX2 = CY(-CZ2-O-Rf-A) (1) (In the formula, X is the same or different -H or F, Y is -H, -F, alkyl group or fluorine-containing alkyl group, and Z is the same or different -H, -F, alkyl group or 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 having an ether bond. A is -COOM, -SO3M, -OSO3M or -C(CF3)2OM (M is -H, a metal atom, -NR) 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (wherein X, Y, and Z are H or organic groups, at least one of them contains a fluorine atom.)

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

[0084] The above-mentioned fluorine-containing alkylene groups having ether bonds with 2 to 100 carbon atoms do not include structures where the oxygen atom is at the terminal end, and are alkylene groups that contain ether bonds between carbon atoms.

[0085] In general formula (1), X is either -H or F. X may be both -F, or at least one of them may be -H. For example, one may be -F and the other -H, or both 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 1 or more carbon atoms. The number of carbon atoms of the alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have 1 or more carbon atoms. The number of carbon atoms of the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. As for Y, -H, -F, or CF3 are preferred, and -F is more preferred.

[0087] In general formula (1), Z is the same or different -H, -F, an alkyl group, or a fluoroalkyl group. The alkyl group is an alkyl group that does not contain a fluorine atom, and may have one or more carbon atoms. The number of carbon atoms of the alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. 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 number of carbon atoms of the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. As Z, -H, -F, or CF3 are 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 general formula (1), Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.

[0090] The number of carbon atoms in the above-mentioned fluorine-containing alkylene group is preferably 2 or more. Furthermore, the number of carbon atoms in the above-mentioned 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. Examples of the above-mentioned fluorine-containing alkylene group include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CF2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, etc. The above-mentioned fluorine-containing alkylene group is preferably a perfluoroalkylene group.

[0091] The number of carbon atoms in the fluorinated alkylene group having the ether bond described above is preferably 3 or more. Furthermore, the number of carbon atoms in the fluorinated alkylene group having the ether bond described above 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 fluorinated alkylene group having the ether bond described above is, for example, a general formula: [ka] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 H or F;Z respectively 4 It is also preferable that is a divalent base represented by H, F, or CF3; p1+q1+r1 is an integer from 1 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5).

[0092] Specific examples of fluorine-containing alkylene groups having the above ether linkage include -CF2CF(CF3)OCF2-, -CF(CF3)CF2-O-CF(CF3)-, and -(CF(CF3)CF2-O). n -CF(CF3)- (where n is an integer from 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) nExamples include -CF(CF3)CH2- (wherein n is an integer from 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. The fluorine-containing alkylene group having the above ether bond is preferably a perfluoroalkylene group.

[0093] In general formula (1), A is -COOM, -SO3M, -OSO3M, or -C(CF3)2OM (where M is H, a metal atom, or NR). 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 ( is H or an organic group).

[0094] R 7 For example, H or C 1-10 The organic group is preferably H or C 1-4 The organic group is more preferably H or C 1-4 A alkyl group is even more preferred.

[0095] Examples of metal atoms include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K, or Li being preferred.

[0096] For M, H, metal atoms, or NR 7 4 is preferred, and H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR 7 4 is more preferred, H, Na, K, Li or NH4 is even more preferred, H, Na, K or NH4 is even more preferred, H, Na or NH4 is particularly preferred, and H or NH4 is most preferred.

[0097] For A, -COOM or -SO3M is preferred.

[0098] Examples of monomers represented by general formula (1) include general formula (1a): CX2 = CFCF2 - O - (CF(CF3)CF2O) n5 -CF(CF3)-A (1a) A monomer represented by (wherein each X is the same and represents either F or H; n5 represents 0 or an integer from 1 to 10; and A is the same as defined above) is given as an example.

[0099] In general formula (1a), n5 is preferably 0 or an integer from 1 to 5, more preferably 0, 1, or 2, and even more preferably 0 or 1, in order to obtain particles with a small primary particle diameter.

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

[0101] The monomer (1) is preferably a monomer represented by the general formula (1A). The polymerization unit (1) is preferably a polymerization unit (1A) based on a monomer represented by general formula (1A). CH2=CF(-CF2-O-Rf-A) (1A) (In the formula, Rf and A are the same as above.)

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

[0103] Specifically, the monomer represented by formula (1A) is the general formula

[0104] [ka]

[0105] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 H or F;Z respectively 4 H, F, or CF3; p1+q1+r1 are integers from 0 to 10; s1 are 0 or 1; t1 are integers from 0 to 5, where Z 3 and Z 4 When both are H, a monomer represented by p1+q1+r1+s1 is not 0 (A is the same as in the definition above) can be given. More specifically,

[0106] [ka]

[0107] These are some of the preferred options, among others

[0108] [ka]

[0109] It is preferable that this be the case.

[0110] The monomer represented by the general formula (1A) is preferably -COOM, and in particular, at least one selected from the group consisting of CH2=CFCF2OCF(CF3)COOM and CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOM (wherein M is the same as defined above), with CH2=CFCF2OCF(CF3)COOM being more preferred.

[0111] Furthermore, monomers represented by general formula (1) include monomers represented by the following formula, etc. CF2 = CFCF2 - O - Rf - A (In the formula, Rf and A are the same as above)

[0112] More specifically, [ka] These are some examples.

[0113] It is also preferable that monomer (I) is monomer (2) represented by general formula (2). Polymer (I) is also preferably polymer (2) which contains polymerization units (2) based on monomers represented by general formula (2). CX2 = CY(-O-Rf-A) (2) (In the formula, X is -H or F, either the same or different; 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 the same as described above.)

[0114] In the method for producing the composition, monomer (2) represented by general formula (2) may be copolymerized with other monomers. Polymer (2) may be a single polymer of monomers represented by general formula (2), or it may be a copolymer with other monomers.

[0115] In general formula (2), X is either -H or F. X may be both -F, or at least one of them may be -H. For example, one may be -F and the other -H, or both may be -H.

[0116] In general formula (2), Y is -H, -F, an alkyl group, or a fluorine-containing alkyl group. An alkyl group is an alkyl group that does not contain a fluorine atom, and may have one or more carbon atoms. The number of carbon atoms of the alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. A fluorine-containing alkyl group is an alkyl group that contains at least one fluorine atom, and may have one or more carbon atoms. The number of carbon atoms of the fluorine-containing alkyl group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. Y is preferably -H, -F, or -CF3, and more preferably -F.

[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 fluorinated alkylene group having 1 to 40 carbon atoms, a fluorinated alkylene group having 2 to 100 carbon atoms and possessing an ether bond, or a fluorinated alkylene group having 2 to 100 carbon atoms and possessing a keto group. Note that the fluorinated alkylene group having 2 to 100 carbon atoms and possessing an ether bond does not include a structure in which the oxygen atom is terminal, and is an alkylene group that contains an ether bond between carbon atoms.

[0119] The number of carbon atoms in the fluorinated alkylene group of Rf is preferably 2 or more. It is also preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 5 or less. Examples of fluorinated alkylene groups include -CF2-, -CH2CF2-, -CF2CF2-, -CF2CH2-, -CF2CF2CH2-, -CF(CF3)-, -CF(CF3)CF2-, -CF(CF3)CH2-, -CF2CF2CF2-, CF2CF2CF2CF2-, etc. The fluorinated alkylene group is preferably a perfluoroalkylene group, and more preferably an unbranched linear perfluoroalkylene group.

[0120] The number of carbon atoms in the fluorinated alkylene group having the ether bond described above is preferably 3 or more. Furthermore, the number of carbon atoms in the fluorinated alkylene group having the ether bond described above is preferably 60 or less, more preferably 30 or less, even more preferably 12 or less, and particularly preferably 5 or less. The fluorinated alkylene group having the ether bond described above is, for example, a general formula: [ka] (In the formula, Z 1 is F or CF3;Z 2 and Z 3 H or F;Z respectively 4It is also preferable that is a divalent base represented by H, F, or CF3; p1+q1+r1 is an integer from 1 to 10; s1 is 0 or 1; t1 is an integer from 0 to 5).

[0121] Specifically, the above fluorine-containing alkylene groups having an ether bond include -CF2CF(CF3)OCF2-, -CF2CF(CF3)OCF2CF2-, -CF2CF(CF3)OCF2CF2CF2-, -CF(CF3)CF2-O-CF(CF3)-, and -(CF(CF3)CF2-O) n -CF(CF3)- (where n is an integer from 1 to 10), -CF(CF3)CF2-O-CF(CF3)CH2-, -(CF(CF3)CF2-O) n Examples include -CF(CF3)CH2- (wherein n is an integer from 1 to 10), -CH2CF2CF2O-CH2CF2CH2-, -CF2CF2CF2O-CF2-, -CF2CF2CF2O-CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CF2-, -CF2CF2CF2O-CF2CF2CH2-, -CF2CF2O-CF2-, -CF2CF2O-CF2CH2-, etc. The fluorine-containing alkylene group having the above ether bond is preferably a perfluoroalkylene group.

[0122] The number of carbon atoms in the fluorinated alkylene group having the keto group is preferably 3 or more. Furthermore, the number of carbon atoms in the fluorinated alkylene group having the 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 the keto group mentioned above include -CF2CF(CF3)CO-CF2-, -CF2CF(CF3)CO-CF2CF2-, -CF2CF(CF3)CO-CF2CF2CF2-, and -CF2CF(CF3)CO-CF2CF2CF2CF2-. The fluorine-containing alkylene group having the keto group is preferably a perfluoroalkylene group.

[0124] Water may be added to the keto group in the fluorine-containing alkylene group. Therefore, monomer (2) may be a hydrate. Examples of fluorine-containing alkylene groups with water added to the keto group include -CF2CF(CF3)C(OH)2-CF2-, -CF2CF(CF3)C(OH)2-CF2CF2-, -CF2CF(CF3)C(OH)2-CF2CF2CF2-, and -CF2CF(CF3)C(OH)2-CF2CF2CF2CF2-.

[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). CF2 = CF - O - (CF2) n1 -A (2a) (In the formula, n1 represents an integer between 1 and 10, and A is the same as described above.) CF2 = CF - O - (CF2C(CF3)F) n2 -A (2b) (In the formula, n² represents an integer between 1 and 5, and A is the same as defined above.) CF2 = CF - O - (CFX 1 ) n3 -A (2c) (In the formula, X 1 (where n3 represents F or CF3, n3 represents an integer from 1 to 10, and A is the same as defined above.) CF2 = CF - O - (CF2CFX) 1 O) n4 -(CF2) n6 -A (2d) (In the formula, n4 represents an integer from 1 to 10, n6 represents an integer from 1 to 3, and A and X 1 (This is the same as the definition above.) CF2 = CF - O - (CF2CF2CFX) 1 O) n5 -CF2CF2CF2-A (2e) (In the formula, n5 represents an integer from 0 to 10, and A and X 1 (This is the same as the definition above.) CF2 = CF - O - (CF2) n7 -O-(CF2) n8 -A (2f) (In the formula, n7 represents an integer from 1 to 10, and n8 represents an integer from 1 to 3. A is the same as defined above.) CF2 = CF[OCF2CF(CF3)] n9 O(CF2) n10 O[CF(CF3)CF2O] n11 CF(CF3)-A (2g) (In the formula, n9 represents an integer from 0 to 5, n10 represents an integer from 1 to 8, and n11 represents an integer from 0 to 5. A is the same as defined above.)

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

[0127] Examples of monomers represented by general formula (2a) include CF2=CF-O-CF2COOM, CF2=CF(OCF2CF2COOM), CF2=CF(O(CF2)3COOM), CF2=CF(OCF2CF2SO3M), CF2=CFOCF2SO3M, and CF2=CFOCF2CF2CF2SO3M (wherein M is the same as defined above).

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

[0129] In general formula (2c), n3 is preferably an integer of 5 or less in terms of water solubility, A is preferably -COOM, and M is preferably H, Na, or NH4.

[0130] In general formula (2d), X 1 In terms of the dispersion stability of the composition, n4 is preferably -CF3, n4 is preferably an integer of 5 or less in terms of water solubility, A is preferably -COOM, and M is preferably H, Na, or NH4.

[0131] Examples of monomers represented by general formula (2d) include CF2=CFOCF2CF(CF3)OCF2CF2COOM, CF2=CFOCF2CF(CF3)OCF2COOM, CF2=CFOCF2CF(CF3)OCF2CF2CF2COOM, CF2=CFOCF2CF(CF3)OCF2SO3M, CF2=CFOCF2CF(CF3)OCF2CF2SO3M, and CF2=CFOCF2CF(CF3)OCF2CF2CF2SO3M (wherein M represents H, NH4, or an alkali metal).

[0132] In general formula (2e), n5 is preferably an integer of 5 or less in terms of water solubility, A is preferably -COOM, and M is preferably H or NH4.

[0133] Examples of monomers represented by the general formula (2e) include CF2 = CFOCF2CF2CF2COOM (wherein M represents H, Na, NH4, or an alkali metal).

[0134] In general formula (2f), n7 is preferably an integer of 5 or less in terms of water solubility, A is preferably -COOM or -SO3M, and more preferably -COOM. M is preferably H, Na, K or NH4.

[0135] Examples of monomers represented by the general formula (2f) include CF2 = CF-O-(CF2)3-O-CF2-COOM (wherein M represents H, NH4, 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, A is preferably -COOM or -SO3M, with -COOM being more preferred, and M is preferably H, Na, K or NH4.

[0137] Examples of monomers represented by the general formula (2g) include CF2=CFO(CF2)2OCF(CF3)COOM, CF2=CFOCF2CF2OCF(CF3)CF2OCF(CF3)COOM, CF2=CFOCF2CF(CF3)OCF2CF2OCF(CF3)COOM, CF2=CF[OCF2CF(CF3)]2O(CF2)2O[CF(CF3)CF2O]CF(CF3)COOM, and CF2=CF[OCF2CF(CF3)]3O(CF2)2O[CF(CF3)CF2O]3CF(CF3)COOM (wherein M represents H, NH4, or an alkali metal).

[0138] It is also preferable that monomer (I) is monomer (3) represented by general formula (3). The polymer (I) is also preferably a polymer (3) that includes polymerization units (3) based on monomers represented by general formula (3). CX2 = CY(-Rf-A) (3) (In the formula, X is either -H or F, either the same or different; 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 possessing an ether bond. A is the same as described above.)

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

[0140] Furthermore, fluorine-containing alkylene groups having ether bonds with 2 to 100 carbon atoms do not include structures where the oxygen atom is at the terminal end, and are alkylene groups that contain ether bonds 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 is preferably a fluorine atom.

[0142] The monomer represented by general formula (3) is general formula (3a): CF2 = CF - (CF2) n1 -A (3a) A monomer represented by (wherein n1 represents an integer from 1 to 10, and A is the same as defined above), and general formula (3b): CF2 = CF - (CF2C(CF3)F) n2 -A (3b) It is preferable to select at least one monomer from the group consisting of monomers represented by (wherein n² represents an integer from 1 to 5, and A is the same as defined above).

[0143] In general formulas (3a) and (3b), A is preferably -SO3M or COOM, and M is H, a metal atom, or NR 7 4. Preferably, it is imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents. 7 represents H or an organic group.

[0144] In general formula (3a), n1 is preferably an integer less than or equal to 5, and more preferably an integer less than or equal to 2. A is preferably -COOM, and M is preferably H or NH4.

[0145] An example of a monomer represented by the general formula (3a) is CF2 = CFCF2COOM (wherein M is the same as defined above).

[0146] In general formula (3b), n2 is preferably an integer of 3 or less in terms of the dispersion stability of the resulting composition, A is preferably -COOM, and M is preferably H or NH4.

[0147] Next, we will describe a preferred configuration for the case where m is an integer greater than or equal to 2 in general formula (I).

[0148] It is also preferable that monomer (I) is at least one selected from the group consisting of monomers represented by general formula (4a) and general formula (4b). The polymer (I) is also preferably a polymer (4) that includes a polymerization unit (4) based on at least one monomer selected from the group consisting of monomers represented by general formula (4a) and general formula (4b). CF2 = CF - CF2 - OQ F1 -CF(-Q F2 -CZ 1 Z 2 -A)2(4a) (In the formula, Z 1 , Z 2 And A is the same as the definition above, Q F1 and Q F2 (These are the same or different fluorinated alkylene groups which may contain single bonds, ether bonds between carbon-carbons, or fluorinated oxyalkylene groups which may contain ether bonds between carbon-carbons.) CF2 = CF - OQ F1 -CF(-Q F2 -CZ 1 Z 2 -A)2(4b) (In the formula, Z 1 , Z 2 A, Q F1 and Q F2 (This is the same as the definition above.)

[0149] The monomers represented by general formulas (4a) and (4b) are: [ka] These are some examples.

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

[0151] In the method for producing the composition, monomer (I) may be copolymerized with other monomers. Polymer (I) may be a homopolymer consisting only of polymerization units (I), or it may be a copolymer containing polymerization units (I) and polymerization units based on other monomers copolymerizable with the monomer represented by general formula (I). From the viewpoint of solubility in aqueous media, a homopolymer consisting only of polymerization units (I) is preferred. Polymerization units (I) may be the same or different in each appearance, and polymer (I) may contain polymerization units (I) based on two or more different monomers represented by general formula (I).

[0152] Other monomers that are preferred include monomers represented by the general formula CFR=CR2 (wherein R is independently H, F, or a perfluoroalkyl group having 1 to 4 carbon atoms). Furthermore, fluorine-containing ethylenic monomers having 2 or 3 carbon atoms are also preferred. Examples of other monomers include CF2=CF2, CF2=CFCl, CH2=CF2, CFH=CH2, CFH=CF2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CHF=CHCF3 (E-isomer), and CHF=CHCF3 (Z-isomer). In particular, at least one selected from the group consisting of tetrafluoroethylene (CF2=CF2), chlorotrifluoroethylene (CF2=CFCl), and vinylidene fluoride (CH2=CF2) is preferred due to its good copolymerizability, and at least one selected from the group consisting of tetrafluoroethylene and vinylidene fluoride is more preferred. Therefore, the polymerization units based on the above other monomers are preferably polymerization units based on tetrafluoroethylene. The polymerization units based on the above other monomers may be the same or different in each appearance, and polymer (I) may contain polymerization units based on two or more different other monomers.

[0153] Other monomers mentioned above include, and also, general formula (n1-2):

[0154] [ka]

[0155] (In the formula, X 1 , X 2 H or F;X are the same or different 3 is H, F, Cl, CH3 or CF3;X 4 , X 5 Rf is either the same or different, H or F; a and c are either the same or different, 0 or 1. 3 Examples include monomers represented by fluorine-containing alkyl groups having 1 to 40 carbon atoms or fluorine-containing alkyl groups having 2 to 100 carbon atoms and ether bonds.

[0156] Specifically, CH2=CFCF2-O-Rf 3 CF2 = CF - O - Rf 3 CF2 = CFCF2 - O - Rf 3 CF2 = CF - Rf 3 CH2=CH-Rf 3 CH2=CH-O-Rf 3 (In the formula, Rf 3 Examples of suitable values ​​include those that are the same as those in the above formula (n1-2).

[0157] Other monomers mentioned above include those in formula (n2-1):

[0158] [ka]

[0159] (In the formula, X 9 is H, F or CH3;Rf 4 Examples include fluorine-containing acrylate monomers represented by 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. 4 The basis is,

[0160] [ka]

[0161] Examples include (where d3 is an integer from 1 to 4; e3 is an integer from 1 to 10) and so on.

[0162] Other monomers mentioned above include those in formula (n2-2): CH2=CHO-Rf 5 (n2-2) (In the formula, Rf 5 Examples include fluorinated vinyl ethers represented by a fluorinated alkyl group having 1 to 40 carbon atoms or a fluorinated alkyl group having 2 to 100 carbon atoms and an ether bond.

[0163] Specifically, as monomers of the general formula (n²-2),

[0164] [ka]

[0165] (where e6 is an integer from 1 to 10) is a preferred example.

[0166] More specifically,

[0167] [ka]

[0168] These are some examples.

[0169] Other general formulas (n2-3): CH2=CHCH2O-Rf 6 (n2-3) (In the formula, Rf 6 Fluorine-containing allyl ethers represented by 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, general formula (n2-4): CH2=CH-Rf 7 (n2-4) (In the formula, Rf 7Examples include fluorine-containing vinyl monomers represented by 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.

[0170] Specifically, monomers represented by general formulas (n2-3) and (n2-4) are:

[0171] [ka]

[0172] Examples of monomers include the following.

[0173] Polymer (I) typically has end groups. These end groups are generated during polymerization, and typical end 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 additional catenary heteroatom. The alkyl or fluoroalkyl group preferably has 1 to 20 carbon atoms. These end groups are generally generated from initiators or chain transfer agents used to form polymer (I), or during the chain transfer reaction.

[0174] In polymer (I), the content of polymerization units (I) 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, relative to the total polymerization units. It is particularly preferable that the content of polymerization units (I) be substantially 100 mol%, and most preferably that polymer (I) consists only of polymerization units (I).

[0175] In 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, relative to the total 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) be substantially 0 mol%, and it is most preferable that polymer (I) does not contain polymerization units based on other monomers.

[0176] The number-average molecular weight of polymer (I) is 0.1 × 10⁻⁶. 4 The above is preferable, 0.2 × 10 4 The above is more preferable, 0.3 × 10 4 The above is even more preferable, 0.4 × 10 4 The above is even more preferable, 0.5 × 10 4 The above is particularly preferable, 1.0 × 10 4 The above is particularly preferred, 3.0 × 10 4 The above is particularly preferred, 3.1 × 10 4 The above is the most preferable. Also, 75.0 × 10 4 The following is preferable: 50.0 × 10 4 The following is more preferable: 40.0 × 10 4 The following is even more preferable: 30.0 × 10 4 The following is particularly preferable: 20.0 × 10 4 The following are particularly preferred. The number-average molecular weight and weight-average molecular weight are values ​​calculated using gel permeation chromatography (GPC) with monodisperse polystyrene as the standard. If GPC measurement is not possible, the number-average molecular weight of polymer (I) can be determined by 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 polymer (I) is, in order of preference, 0.2 × 10⁻⁶.4 The above is 0.4 × 10 4 The above is 0.6 × 10 4 The above is 0.8 × 10 4 The above is 1.0 × 10 4 The above is 2.0 × 10 4 The above is 5.0 x 10 4 The above is 10.0 × 10 4 The above is 15.0 × 10 4 The above is 20.0 × 10 4 The above is 25.0 × 10 4 That concludes the explanation. Furthermore, the upper limit of the weight-average molecular weight of polymer (I) is, in order of preference, 150.0 × 10⁻⁶. 4 Below, 100.0 × 10 4 Below, 60.0 × 10 4 Below, 50.0 × 10 4 Below, 40.0 × 10 4 The following applies:

[0178] Polymer (I) preferably has an ion exchange rate (IXR) of 53 or less. The IXR is defined as the number of carbon atoms in the polymer backbone relative to the ionic group. Precursor groups that become ionic by hydrolysis (e.g., -SO2F) are not considered ionic groups for the purpose of determining the IXR.

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

[0180] The ion exchange capacity of 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, greater 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 polymer (I) and can be calculated from the composition of polymer (I).

[0181] In polymer (I), ionic groups (anionic groups) are typically distributed along the polymer backbone. The polymer (I) preferably includes the polymer backbone together with repeating side chains bonded to this backbone, and these side chains have ionic groups.

[0182] Polymer (I) preferably contains ionic groups having a pKa of less than 10, more preferably less than 7. The ionic groups of polymer (I) are preferably selected from the group consisting of sulfonates, carboxylates, phosphonates, and phosphates.

[0183] The terms "sulfonate, carboxylate, phosphonate, and phosphate" are intended to refer to their respective salts, or the respective acids that can form salts. When salts are used, they are preferably alkali metal salts or ammonium salts. Preferred ionic groups are carboxylate groups and sulfonate groups.

[0184] Polymer (I) is preferably water-soluble. Water solubility means the property of readily dissolving or dispersing in an aqueous medium. For example, water-soluble polymer (I) may not have a particle size that can be measured by dynamic light scattering (DLS), or may exhibit a particle size of 10 nm or less.

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

[0186] The viscosity of an aqueous solution of polymer (I) can be determined by adjusting the polymer (I) content in the aqueous solution to 33% by mass relative to the aqueous solution, and then measuring the viscosity of the resulting aqueous solution at 20°C using a tuning fork vibratory viscometer (model: SV-10) manufactured by A&D Company, Limited.

[0187] The critical micelle concentration (CMC) of 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, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0188] The critical micelle concentration of polymer (I) can be determined by measuring its surface tension. Surface tension can be measured, for example, using a surface tension meter, model CBVP-A3, manufactured by Kyowa Interface Chemical Co., Ltd.

[0189] The acid value of polymer (I) is preferably 60 or higher, more preferably 90 or higher, even more preferably 120 or higher, particularly preferably 150 or higher, most preferably 180 or higher, and there is no particular upper limit, but it is preferably 300 or lower.

[0190] The acid value of polymer (I) is determined by whether polymer (I) has anionic groups other than acidic functional groups, such as -COOM, -SO3M, -OSO3M, or -C(CF3)2OM (where M is a metal atom, NR). 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 If the substance has H or an organic group, these groups can be converted to acidic groups and then measured by acid-base titration.

[0191] As polymer (I), a polymer (11) of monomer (11) represented by general formula (11), wherein the content of polymerization units (11) based on monomer (11) is 50 mol% or more relative to the total polymerization units constituting polymer (11), and the weight-average molecular weight (Mw) is 38.0 × 10⁻⁶. 4The polymer (11) described above can also be used. Polymer (11) is a novel polymer. General formula (11): CX2=CY-CF2-O-Rf-A (In the formula, X and Y are independently H, F, CH3, or CF3, and at least one of X and Y is F. Rf is a fluorinated alkylene group having 1 to 40 carbon atoms, or a fluorinated alkylene group having 2 to 100 carbon atoms and an ether bond. A is -COOM, -SO3M, -OSO3M, or -C(CF3)2OM (M is H, a metal atom, NR) 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (This is either H or an organic group.)

[0192] In general formula (11), X and Y are independently H, F, CH3, or CF3, 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] The Rf and A in general formula (11) are the same as the Rf and A in general formula (1) that represent the monomers constituting polymer (1).

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

[0195] The content of polymerization units (11) in the polymer (11) is, in order of 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, relative to the total polymerization units constituting the polymer (11). The content of polymerization units (11) is particularly preferably substantially 100 mol%, and it is most preferable that the polymer (11) consists only of polymerization units (11).

[0196] In polymer (11), the content of polymerization 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, relative to the total polymerization units constituting polymer (11). It is particularly preferable that the content of polymerization units based on other monomers copolymerizable with monomer (11) be substantially 0 mol%, and it is most preferable that polymer (11) does not contain polymerization units based on other monomers.

[0197] The lower limit of the weight-average molecular weight of polymer (11) is, in order of preference, 38.0 × 10⁶. 4 The above is 40.0 × 10 4 That concludes the explanation. The upper limit of the weight-average molecular weight of polymer (11) is, in order of preference, 150.0 × 10⁻⁶. 4 Below, 100.0 × 10 4 Below, 60.0 × 10 4 That is the case.

[0198] The lower limit of the number-average molecular weight of polymer (11) is, in order of preference, 5.0 × 10 4 , 8.0×10 4 , 10.0×10 4 The above is 12.0 × 10 4 That concludes the explanation. The upper limit of the number-average molecular weight of polymer (11) is, in order of preference, 75.0 × 10 4 Below, 50.0 × 10 4 Below, 40.0 × 10 4 Below, 30.0 × 10 4 The following applies:

[0199] The polymer (I) is a polymer (12) of monomer (12) represented by general formula (12), wherein the content of polymerization units (12) based on monomer (12) is 50 mol% or more relative to the total polymerization units constituting the polymer (12), and the weight-average molecular weight (Mw) is 1.4 × 10⁻⁶. 4 The polymer (12) described above can also be used. Polymer (12) is a novel polymer. General formula (12): CX2=CX-O-Rf-A (In the formula, X is independently F or CF3, Rf is a fluorinated alkylene group having 1 to 40 carbon atoms, or a fluorinated alkylene group having an ether bond or keto group having 2 to 100 carbon atoms. A is -COOM, -SO3M, -OSO3M, or -C(CF3)2OM (M is -H, a metal atom, -NR) 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (This is either H or an organic group.)

[0200] In general formula (12), X is independently F or CF3. It is preferable that at least one X is F, and more preferable that all X are F.

[0201] The Rf and A in general formula (12) are the same as the Rf and A in general formula (2) that represent the monomers constituting polymer (2).

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

[0203] The content of polymerization 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, relative to the total polymerization units constituting the polymer (12). The content of polymerization units (12) is particularly preferably substantially 100 mol%, and it is most preferable that the polymer (12) consists only of polymerization units (12).

[0204] In polymer (12), the content of polymerization units based on other monomers copolymerizable with monomer (12) is, in order of 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, relative to the total polymerization units constituting polymer (12). It is particularly preferable that the content of polymerization units based on other monomers copolymerizable with monomer (12) be substantially 0 mol%, and it is most preferable that polymer (12) does not contain polymerization units based on other monomers.

[0205] The lower limit of the weight-average molecular weight (Mw) of polymer (12) is, in order of preference, 1.4 × 10⁻⁶. 4 The above is 1.7 × 10 4 The above is 1.9 × 10 4 The above is 2.1 × 10 4 The above is 2.3 × 10 4 The above is 2.7 × 10 4 The above is 3.1 × 10 4 The above is 3.5 × 10 4 The above is 3.9 × 10 4 The above is 4.3 × 10 4 The above is 4.7 × 10 4 The above is 5.1 × 10 4 That concludes the explanation. The upper limit of the weight-average molecular weight (Mw) of polymer (12) is, in order of preference, 150.0 × 10⁻⁶. 4 Below, 100.0 × 10 4 Below, 60.0 × 10 4 Below, 50.0 × 10 4 Below, 40.0 × 10 4 The following applies:

[0206] The lower limit of the number-average molecular weight (Mn) of the polymer (12) is, in order of preference, 0.7 × 10⁻⁶. 4 The above is 0.9 × 10 4 The above is 1.0 × 10 4 The above is 1.2 × 10 4 The above is 1.4 × 10 4 The above is 1.6 × 10 4 The above is 1.8 × 10 4 That concludes the explanation. The upper limit for the number-average molecular weight (Mn) of polymer (12) is, in order of preference, 75.0 × 10⁻⁶. 4 Below, 50.0 × 10 4 Below, 40.0 × 10 4 Below, 30.0 × 10 4 Below, 20.0 × 10 4 The following applies:

[0207] The molecular weight distribution (Mw / Mn) of 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 polymerization units (12) and polymerization units based on other monomers copolymerizable with monomer (12), the content of polymerization units (12) based on monomer (12) is preferably 40 to 60 mol%, more preferably 45 to 55 mol%, relative to the total polymerization units constituting the polymer (12), and the content of polymerization units based on other monomers is preferably 60 to 40 mol%, more preferably 55 to 45 mol%, relative to the total polymerization units constituting the polymer (12). Such a configuration is particularly suitable when the polymerization units based on other monomers copolymerizable with monomer (12) are polymerization units (M) based on monomers represented by the general formula CFR=CR2.

[0209] When the polymer (12) contains polymerization units (12) and polymerization units based on other monomers copolymerizable with monomer (12), the alternation ratio between polymerization units (12) and polymerization units based on other monomers copolymerizable with 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 particularly suitable when the polymerization units based on other monomers copolymerizable with monomer (12) are polymerization units (M) based on monomers represented by the general formula CFR=CR2.

[0210] The ratio of polymerization units (12) and polymerization units based on monomers (12) and other copolymerizable monomers in the polymer (12) is 19 This can be determined by F-NMR analysis.

[0211] Polymer (I) can be produced by conventionally known methods, except for the use of the monomers described above.

[0212] As polymer (I), a polymer (13) of monomer (13) represented by general formula (13) can also be used, wherein the content of polymerization units (13) based on monomer (13) is 50% by mass or more relative to the total polymerization units constituting polymer (13). Polymer (13) is a novel polymer. General formula (13): CX2=CX-O-Rf-SO3M (In the formula, X is independently F or CF3, Rf is a fluorinated alkylene group having 1 to 40 carbon atoms, or a fluorinated alkylene group having an ether bond or keto group having 2 to 100 carbon atoms. M is -H, a metal atom, -NR) 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (This is either H or an organic group.)

[0213] In general formula (13), X is independently F or CF3. It is preferable that at least one X is F, and more preferable that all X are F.

[0214] The Rf and M in general formula (13) are the same as the Rf and A in general formula (2) that represent the monomers constituting polymer (2).

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

[0216] The polymer (13) has a content of polymerization units (13) based on monomers (13) of 50% by mass or more relative to the total polymerization units constituting the polymer (13). The content of polymerization units (13) in 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, relative to the total polymerization units constituting the polymer (13). It is particularly preferable that the content of polymerization units (13) be substantially 100% by mass, and it is most preferable that the polymer (13) consists only of polymerization units (13).

[0217] In polymer (13), the content of polymerization units based on other monomers copolymerizable with monomer (13) is, in order of 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, relative to the total polymerization units constituting polymer (13). It is particularly preferable that the content of polymerization units based on other monomers copolymerizable with monomer (13) be substantially 0% by mass, and it is most preferable that polymer (13) does not contain polymerization units based on other monomers.

[0218] The lower limit of the number-average molecular weight of polymer (13) is, in order of preference, 0.3 × 10⁻⁶. 4 The above is 0.4 × 10 4 The above is 0.5 × 10 4 The above is 0.7 × 10 4 The above is 0.8 × 10 4 The above is 1.0 × 10 4 The above is 1.2 × 10 4 The above is 1.4 × 10 4 , 1.6×10 4 The above is 1.8 × 10 4 The above is 2.0 × 10 4 The above is 3.0 × 10 4 That concludes the explanation. The upper limit of the number-average molecular weight of polymer (13) is, in order of preference, 75.0 × 10 4 Below, 50.0 × 10 4 Below, 40.0 × 10 4 Below, 30.0 × 10 4 Below, 20.0 × 10 4 The following applies:

[0219] The lower limit of the weight-average molecular weight of polymer (13) is, in order of preference, 0.4 × 10⁻⁶. 4 The above is 0.5 × 10 4 The above is 0.6 × 10 4 The above is 0.8 × 10 4 The above is 1.0 × 10 4 The above is 1.2 × 10 4 The above is 1.4 × 10 4 The above is 1.7 × 10 4 The above is 1.9 × 10 4 The above is 2.1 × 10 4 The above is 2.3 × 10 4 The above is 2.7 × 10 4 The above is 3.1 × 10 4 The above is 3.5 × 10 4 The above is 3.9 × 10 4 The above is 4.3 × 10 4 The above is 4.7 × 10 4 The above is 5.1 × 10 4 The above is 10.0 × 10 4 The above is 15.0 × 10 4 The above is 20.0 × 10 4 The above is 25.0 × 10 4That concludes the explanation. The upper limit of the weight-average molecular weight of polymer (13) is, in order of preference, 150.0 × 10⁻⁶. 4 Below, 100.0 × 10 4 Below, 60.0 × 10 4 Below, 50.0 × 10 4 Below, 40.0 × 10 4 The following applies:

[0220] The molecular weight distribution (Mw / Mn) of polymer (13) is, in order of preference, 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), polymer (11) is a novel polymer, and the polymer (11) can be produced by polymerizing monomer (11) represented by general formula (11) in an aqueous medium, wherein the polymer (11) can be produced by a production method (11) that maintains the oxygen concentration in the polymerization reaction system at 500 ppm by volume or less.

[0222] In manufacturing method (11), the oxygen concentration in the polymerization reaction system is 500 ppm by volume or less. In manufacturing 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. In addition, the oxygen concentration in the reaction system is usually 0.01 ppm by volume or more.

[0223] In the manufacturing 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, particularly preferably 53°C or lower, 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, in order to easily produce a polymer (11) with an even higher molecular weight.

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

[0225] In the manufacturing method (11), 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.

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

[0227] Of the polymers (I), polymer (12) is a novel polymer, and the polymer (12) can be produced by polymerizing monomer (12) represented by general formula (12) in an aqueous medium, wherein the polymer (12) can be produced by a production method (12) that maintains the oxygen concentration in the polymerization reaction system at 1500 ppm by volume or less.

[0228] In manufacturing method (12), the oxygen concentration in the polymerization reaction system is 1500 ppm by volume or less. In manufacturing 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] Of the polymers (I), polymer (13) is a novel polymer and can be produced by a polymer (13) production method (13) which produces polymer (13) of monomer (13) by polymerizing monomer (13) represented by general formula (13) in an aqueous medium.

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

[0231] In manufacturing methods (12) and (13), the polymerization temperature of monomer (12) and 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, especially 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, in order to easily produce polymers (12) and polymers (13) with even higher molecular weights.

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

[0233] In manufacturing methods (12) and (13), the polymerization pressure is typically 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 manufacturing methods (12) and (13), the polymerization time is usually 1 to 200 hours, but may be 5 to 100 hours.

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

[0236] In manufacturing methods (11) to (13), the aqueous medium means a reaction medium for polymerization, which is a liquid containing water. The aqueous medium is not particularly limited as long as it contains water, and may contain water and, for example, a fluorine-free organic solvent such as an alcohol, ether, or ketone, and / or a fluorine-containing organic solvent with a boiling point of 40°C or less. Water is preferred as the aqueous medium.

[0237] In manufacturing methods (11) to (13), monomer polymerization 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 polymerization temperature range, and known oil-soluble and / or water-soluble polymerization initiators can be used. Furthermore, polymerization can also be initiated as a redox by combining it with a reducing agent, etc. The concentration of the polymerization initiator is appropriately determined depending on the type of monomer, the molecular weight of the target polymer, and the reaction rate.

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

[0239] As polymerization initiators, persulfates are preferred because they allow for the easy production of polymers with even higher molecular weights. Examples of persulfates include ammonium persulfate, potassium persulfate, and sodium persulfate, with ammonium persulfate being preferred.

[0240] There are no particular limitations on the amount of polymerization initiator added, but it is sufficient to add at least an amount that does not significantly reduce the polymerization rate (for example, a few ppm relative to water concentration) in one lump sum at the beginning of polymerization, or sequentially or continuously. The upper limit is a range in which the reaction temperature can be increased while removing heat from the apparatus surface using the heat of the polymerization reaction, and a more preferable upper limit is a range in which the heat of the polymerization reaction can be removed from the apparatus surface.

[0241] In manufacturing methods (11) to (13), the polymerization initiator can be added at the start of polymerization and 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; the entire amount may be added at once, divided into two or more additions, or added continuously.

[0242] In manufacturing methods (11) to (13), polymers with even higher molecular weights can be easily produced, so it is preferable that the total amount of polymerization initiator added for polymerization is 0.00001 to 10% by mass relative to the aqueous medium. The total amount of polymerization initiator added for 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 manufacturing methods (11) to (13), polymers with even higher molecular weights can be easily produced, so it is preferable that the total amount of polymerization initiator added for polymerization is 0.001 to 10 mol% relative to the monomer. The total amount of polymerization initiator added for 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 manufacturing methods (11) to (13), polymers with even higher molecular weights can be easily produced, so it is preferable that the amount of monomers containing monomers (11) to (13) at the start of polymerization is 30% by mass or more relative to the amount of aqueous medium. The amount of monomers is more preferably 30% by mass or more, and even more preferably 40% by mass or more. There is no particular upper limit to the amount of monomers, but from the viewpoint of ensuring smooth polymerization, it may be 200% by mass or less. The amount of monomers at the start of polymerization refers to the total amount of monomers (11) to (13) and any other monomers present in the reactor at the start of polymerization.

[0245] In manufacturing methods (11) to (13), polymerization may be carried out in the presence of a pH adjusting agent. The pH adjusting agent may be added before the start of polymerization or after the start of polymerization.

[0246] As pH adjusters, 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, ammonium gluconate, etc. can be used.

[0247] In manufacturing methods (11) to (13), polymerization of monomers (11) to (13) can be carried out by charging an aqueous medium, one of monomers (11) to (13), and other monomers and other additives as needed into a reactor, stirring the contents of the reactor, maintaining the reactor at a predetermined polymerization temperature, and then adding a predetermined amount of polymerization initiator to start the polymerization reaction. After the start of the polymerization reaction, monomers, polymerization initiators, and other additives may be added as needed.

[0248] In manufacturing methods (11) to (13), monomer polymerization can be carried out substantially in the absence of a fluorine-containing surfactant. In this disclosure, "substantially in the absence of a fluorine-containing surfactant" means that the amount of fluorine-containing surfactant in the aqueous medium is 10 ppm by mass or less. The amount of fluorine-containing surfactant in 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] With regard to fluorine-containing surfactants, the information explained in the description of polymerization of fluoromonomers can also be applied to the manufacturing methods (11) to (13).

[0250] The content of dimers and trimers of monomer (I) represented by 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, relative to polymer (I).

[0251] (Fluororubber) The compositions disclosed herein contain fluororubber.

[0252] Fluororubber is preferably having an ion exchange rate (IXR) higher than 53. Preferred fluororubber is either completely free of ionic groups or has a limited number of ionic groups that result in an ion exchange rate higher than about 100. The ion exchange rate of preferred fluororubber is preferably 1000 or higher, more preferably 2000 or higher, and even more preferably 5000 or higher.

[0253] The fluororubber in the composition of the present disclosure can be produced, for example, by the following method. That is, polymerization of fluororubber is carried out by charging pure water and polymer (I) into a pressure-resistant reaction vessel equipped with a stirrer, deoxygenating it, charging the monomer, raising it to a predetermined temperature, and adding a polymerization initiator to start the reaction. As the reaction progresses, the pressure decreases, so additional monomer is continuously or intermittently supplied to maintain the initial pressure. When a predetermined amount of monomer has been supplied, the supply is stopped, the monomer in the reaction vessel is 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 manufacturing the above-mentioned fluororubber, it is also possible to use a method that allows for a faster final polymerization rate compared to conventional polymerization, by first synthesizing fluoropolymer fine particles at the above-mentioned high concentration, then diluting them and further polymerization, as disclosed in International Publication No. 00 / 01741.

[0255] The polymerization of the above-mentioned fluororubber is carried out under conditions that are appropriately selected from the viewpoint of the physical properties of the target polymer and the polymerization rate control, but 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. Furthermore, it is preferable to maintain the pH of the polymerization medium at 1.5 to 13 using pH adjusting agents, etc., as described later, by known methods.

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

[0257] The fluoromonomers used in the polymerization of the above-mentioned fluororubber are preferably those having at least one double bond. Examples of such fluoromonomers include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], vinyl fluoride, vinylidene fluoride [VDF], trifluoroethylene, fluoroalkyl vinyl ether, fluoroalkylethylene, fluoroalkyl allyl ether, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, and general formula (100):CHX 101 =CX 102 Rf 101 (In the formula, X 101 and X 102 In this case, one side is H, the other is F, and Rf 101 Preferably, the monomer is at least one selected from the group consisting of fluoromonomers (represented by a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), fluorinated vinyl heterocyclic compounds, and monomers that provide a crosslinking site.

[0258] Examples of the above fluoroalkyl vinyl ethers are, General formula (110): CF2=CF-ORf 111 (In the formula, Rf 111 represents a perfluoroorganic group. ) Fluoromers represented by ) General formula (120): CF2=CF-OCH2-Rf 121 (In the formula, Rf 121 Fluoromers represented by perfluoroalkyl groups having 1 to 5 carbon atoms, General formula (130): CF2=CFOCF2ORf 131 (In the formula, Rf 131 These are fluoromonomers represented by ( ), which are linear or branched perfluoroalkyl groups having 1 to 6 carbon atoms, cyclic perfluoroalkyl groups having 5 to 6 carbon atoms, or linear or branched perfluorooxyalkyl groups having 2 to 6 carbon atoms containing 1 to 3 oxygen atoms. General formula (140): CF2=CFO(CF2CF(Y 141 )O) m (CF2) n F (In the formula, Y 141 represents a fluorine atom or a trifluoromethyl group. m is an integer from 1 to 4. n is an integer from 1 to 4. ) Fluoromers represented by ), and General formula (150): CF2=CF-O-(CF2CFY 151 -O) n -(CFY 152 ) m -A 151 (In the formula, Y 151 Y represents a fluorine atom, a chlorine atom, a -SO2F group, or a perfluoroalkyl group. The perfluoroalkyl group may contain etheric oxygen and a -SO2F group. n represents an integer from 0 to 3. n Y 151 They may be the same or different. 152 represents a fluorine atom, a chlorine atom, or a -SO2F group. m represents an integer from 1 to 5. m Y 152They may be the same or they may be different. 151 is, -SO2X 151 ,-COZ 151 or -POZ 152 Z 153 It represents X. 151 F, Cl, Br, I, -OR 151 or -NR 152 R 153 Represents Z 151 , Z 152 and Z 153 These are the same or different, -NR 154 R 155 OR 156 Represents R 151 , R 152 , R 153 , R 154 , R 155 and R 156 ) represents a fluoromonomer that may contain the same or different H, ammonium, alkali metal, fluorine atom, alkyl group, aryl group, or sulfonyl-containing group. It is preferable that it be at least one selected from the group consisting of the following:

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

[0260] As a fluoromonomer represented by general formula (110), Rf 111 Examples of fluoromonomers include those in which the perfluoroalkyl group has 1 to 10 carbon atoms. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 5.

[0261] Examples of perfluoroorganic groups in general formula (110) include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, and perfluorohexyl groups. As a fluoromonomer represented by general formula (110), further, in the above general formula (110), Rf111 Those in which the group is a perfluoro(alkoxyalkyl) group with 4 to 9 carbon atoms, Rf 111 The formula is as follows:

[0262] [ka]

[0263] The base represented by (wherein m represents an integer from 0 to 4) is given by the following formula:

[0264] CF3CF2CF2-(O-CF(CF3)-CF2) n - Examples include the base represented by (wherein n represents an integer from 1 to 4).

[0265] Among the fluoromonomers represented by general formula (110), General formula (160): CF2=CF-ORf 161 (In the formula, Rf 161 represents a perfluoroalkyl group having 1 to 10 carbon atoms. Fluoromonomers represented by ) are preferred. Rf 161 It is preferable that it is 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 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 general formula (130) is preferably at least one selected from the group consisting of CF2=CFOCF2OCF3, CF2=CFOCF2OCF2CF3, and CF2=CFOCF2OCF2CF2OCF3.

[0269] The fluoromonomer represented by general formula (140) is preferably at least one selected from the group consisting of CF2=CFOCF2CF(CF3)O(CF2)3F, CF2=CFO(CF2CF(CF3)O)2(CF2)3F, and CF2=CFO(CF2CF(CF3)O)2(CF2)2F.

[0270] As the fluoromonomer represented by general formula (150), at least one selected from the group consisting of CF2=CFOCF2CF2SO2F, CF2=CFOCF2CF(CF3)OCF2CF2SO2F, CF2=CFOCF2CF(CF2CF2SO2F)OCF2CF2SO2F, and CF2=CFOCF2CF(SO2F)2 is preferred.

[0271] As a fluoromonomer represented by the general formula (100), Rf 101 A fluoromonomer that is a straight-chain fluoroalkyl group is preferred, and Rf 101 A fluoromonomer in which the linear perfluoroalkyl group is is more preferred. 101 The carbon number of the compound is preferably 1 to 6. Examples of fluoromonomers represented by general formula (100) include CH2=CFCF3, CH2=CFCF2CF3, CH2=CFCF2CF2CF3, CH2=CFCF2CF2CF2H, CH2=CFCF2CF2CF2CF3, CHF=CHCF3 (E isomer), CHF=CHCF3 (Z isomer), and among these, 2,3,3,3-tetrafluoropropylene represented by CH2=CFCF3 is preferred.

[0272] As for fluoroalkylethylenes, General formula (170): CH2=CH-(CF2) n -X 171 (In the formula, X171 is H or F, and n is an integer from 3 to 10. Fluoroalkylethylenes represented by ) are preferred, such as CH2=CH-C4F9 and CH2=CH-C6F 13 It is more preferable that it be at least one selected from the group consisting of the following:

[0273] Examples of the above fluoroalkylallyl ethers are, General formula (180): CF2=CF-CF2-ORf 111 (In the formula, Rf 111 ) represents a perfluoroorganic group. Examples include fluoromonomers represented by ).

[0274] Rf of general formula (180) 111 Rf of general formula (110) 111 It is the same as Rf 111 As such, a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkoxyalkyl group having 1 to 10 carbon atoms is preferred. As the fluoroalkyl allyl ether represented by general formula (180), at least one selected from the group consisting of CF2=CF-CF2-O-CF3, CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9 is preferred, at least one selected from the group consisting of CF2=CF-CF2-O-C2F5, CF2=CF-CF2-O-C3F7, and CF2=CF-CF2-O-C4F9 is more preferred, and CF2=CF-CF2-O-CF2CF2CF3 is even more preferred.

[0275] The above fluorinated vinyl heterocyclic material is a general formula (230): [ka] (In the formula, X 231 and X 232 These are independently F, Cl, a methoxy group, or a fluorinated methoxy group, and Y 231 is equation Y 232 or formula Y 233 That is the case.

[0276] [ka] (In the formula, Z 231 and Z 232 A fluorinated vinyl heterocyclic compound represented by )) is independently F or a fluorinated alkyl group having 1 to 3 carbon atoms.

[0277] As monomers that provide crosslinking sites, General formula (180):CX 181 2=CX 182 -R f 181 CHR 181 X 183 (In the formula, X 181 and X 182 These are independently a hydrogen atom, a fluorine atom, or CH3, R f 181 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group or a perfluoro(poly)oxyalkylene group, R 181 is a hydrogen atom or CH3, X 183 ) is an iodine atom or a bromine atom. ) Fluoromers represented by General formula (190):CX 191 2=CX 192 -R f 191 X 193 (In the formula, X 191 and X 192 These are independently a hydrogen atom, a fluorine atom, or CH3, R f 191 X is a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group, or a perfluoropolyoxyalkylene group. 193 ) is an iodine atom or a bromine atom. ) Fluoromers represented by General formula (200): CF2=CFO(CF2CF(CF3)O) m (CF2) n -X 201 (In the formula, m is an integer from 0 to 5, n is an integer from 1 to 3, X 201) is a fluoromonomer represented by a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2I, and General formula (210): CH2=CFCF2O(CF(CF3)CF2O) m (CF(CF3)) n -X 211 (In the formula, m is an integer from 0 to 5, n is an integer from 1 to 3, X 211 ) is a fluoromonomer represented by a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2OH, and 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 These are either the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. 221 This includes linear or branched alkylene groups having 1 to 18 carbon atoms, cycloalkylene groups having 3 to 18 carbon atoms, alkylene groups or oxyalkylene groups having 1 to 10 carbon atoms that are at least partially fluorinated, or -(Q) p -CF2O-(CF2CF2O) m (CF2O) n -CF2-(Q) p - A monomer represented by (wherein Q is an alkylene group or an oxyalkylene group, p is 0 or 1, and m / n is 0.2 to 5) and having a molecular weight of 500 to 10000. It is preferable that it be at least one selected from the group consisting of the following:

[0278] X 183 and X 193It is preferable that R is an iodine atom. f 181 and R f 191 It is preferable that it is a perfluoroalkylene group having 1 to 5 carbon atoms. 181 It is preferably a hydrogen atom. 201 It is preferable that this is a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2I. 211 It is preferable that the component is a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2OH.

[0279] The monomers that provide the crosslinking site are CF2=CFOCF2CF(CF3)OCF2CF2CN, CF2=CFOCF2CF(CF3)OCF2CF2COOH, CF2=CFOCF2CF(CF3)OCF2CF2CH2I, CF2=CFOCF2CF2CH2I, CH2=CFCF2OCF(CF3)CF2OCF(CF3)CN, CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOH, CH2=CFCF2OCF( It is preferable that it is at least one selected from the group consisting of CF3)CF2OCF(CF3)CH2OH, CH2=CHCF2CF2I, CH2=CH(CF2)2CH=CH2, CH2=CH(CF2)6CH=CH2, and CF2=CFO(CF2)5CN, and more preferably at least one selected from the group consisting of CF2=CFOCF2CF(CF3)OCF2CF2CN and CF2=CFOCF2CF2CH2I.

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

[0281] In the polymerization of the above-mentioned fluororubber, known inorganic radical polymerization initiators can be used as polymerization initiators. Among the inorganic radical polymerization initiators, conventionally known water-soluble inorganic peroxides, such as sodium, potassium, and ammonium persulfates, superphosphates, perborates, percarbonates, or permanganates, are particularly useful. These radical polymerization initiators can be further activated by reducing agents, such as sodium, potassium, or ammonium sulfites, bisulfites, metabisulfites, hyposulfites, thiosulfates, phosphites, or hypophosphites, or by readily 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 preferable to use ammonium persulfate together with 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, based on 100% by mass of the total amount of monomer.

[0283] In the polymerization of the above-mentioned fluororubber, known chain transfer agents can be used, but hydrocarbons, esters, ethers, alcohols, ketones, chlorine compounds, carbonates, iodine compounds, etc., can be used. Among these, isopentane, diethyl malonate, and ethyl acetate are preferred from the viewpoint of not reducing the reaction rate, and iodine compounds such as I(CF2)4I, I(CF2)6I, and ICH2I are preferred from the viewpoint of enabling iodination of the polymer ends and being usable as reactive polymers.

[0284] The amount of the above-mentioned chain transfer agent used is typically 0.5 × 10⁻⁶ of the total amount of monomer supplied. -3 ~5×10 -3 mol%, preferably 1.0 × 10 -3 ~3.5×10 -3 It is preferable that it be in mol%.

[0285] In the polymerization of the above-mentioned fluororubber, phosphates, sodium hydroxide, potassium hydroxide, etc., can preferably be used as pH adjusting agents.

[0286] The polymerization dispersion obtained by the composition manufacturing method has a solid content 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 at the time polymerization is completed.

[0287] Among fluororubbers, perfluororubber (perfluoroelastomer) is obtained by polymerizing perfluoromonomers in an aqueous medium in the presence of polymer (I).

[0288] As perfluoro monomers, Tetrafluoroethylene (TFE), Hexafluoropropylene [HFP] General formula: CF2=CF-ORf 13 (In the formula, Rf 13 ) represents a perfluoroalkyl group having 1 to 8 carbon atoms. General formula: CF2=CFOCF2ORf 14 (In the formula, Rf 14 Fluoromers represented by (a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or a linear or branched perfluorooxyalkyl group having 2 to 6 carbon atoms containing 1 to 3 oxygen atoms), and General formula: CF2=CFO(CF2CF(Y 15 )O) m (CF2) n F (In the formula, Y 15 represents a fluorine atom or a trifluoromethyl group. m is an integer from 1 to 4. n is an integer from 1 to 4. ) Fluoromer represented by At least one selected from the group consisting of is preferred.

[0289] Furthermore, in the polymerization of perfluoromonomers, monomers that provide crosslinking sites may be polymerized together with the perfluoromonomers.

[0290] In the method for producing perfluoroelastomers, the polymer (I) used preferably has an ion exchange capacity of 1.50 meq / g or more. The ion exchange capacities of 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 polymer (I) and can be calculated from the composition of polymer (I). Precursor groups that become ionic by hydrolysis (for example, -COOCH3) are not considered ionic groups for the purpose of determining the ion exchange capacity. It is presumed that a higher ion exchange capacity of polymer (I) means that polymer (I) has more anionic groups, resulting in the formation of highly stable particles, and because of the high particle-forming ability, the number of particles per unit amount of water increases, leading to a higher polymerization rate.

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

[0292] The amount of polymer (I) added is preferably 0.1% by mass or more, even 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, based on 100% by mass of the aqueous medium, in order to facilitate the polymerization reaction of the perfluoromonomers.

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

[0294] The polymerization of perfluoromonomers 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, based on 100% by mass of perfluoromonomer. By keeping the amount of polymerization initiator added (amount present) in the above polymerization within the above range, the polymerization reaction of perfluoromonomers proceeds smoothly, and perfluoroelastomers can be produced efficiently. If the amount of polymerization initiator added is too small, a sufficient polymerization rate or sufficient yield may not be obtained.

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

[0296] As pH adjusters, ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium phosphate, potassium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, dipotassium dihydrogen phosphate, sodium citrate, potassium citrate, ammonium citrate, sodium gluconate, potassium gluconate, ammonium gluconate, etc. can be used.

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

[0298] Fluoromers used to obtain partially fluorinated rubber include vinylidene fluoride (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 ether, and general formula: CHX. 1 =CX 2 Rf (where X 1 and X 2 Preferably, at least one selected from the group consisting of fluorine-containing monomers (2) (where one is H and the other is F, and Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms).

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

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

[0301] The amount of polymer (I) added is preferably 0.0001% by mass or more, even more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, particularly preferably 0.005% by mass or more, most preferably 0.01% by mass or more, based on 100% by mass of the aqueous medium, in order to facilitate the polymerization reaction of the fluoromonomers.

[0302] Furthermore, regarding the amount of polymer (I) added, if the amount added is too large, the effect commensurate with the amount added will not be obtained, which is economically disadvantageous. Therefore, the amount 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, based on 100% by mass of the aqueous medium.

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

[0304] The above-mentioned fluororubber may be partially fluorinated rubber or perfluororubber.

[0305] Partially fluorinated rubber preferably contains a methylene group (-CH2-) in its main chain. Partially fluorinated rubber containing -CH2- in its main chain is not particularly limited as long as it contains a chemical structure represented by -CH2-, and examples include partially fluorinated rubber containing structures such as -CH2-CF2-, -CH2-CH(CH3)-, -CH2-CH2-, and -CH2-CF(CF3)-, which can be introduced into the main chain of the partially fluorinated rubber by polymerizing vinylidene fluoride, propylene, ethylene, 2,3,3,3-tetrafluoropropylene, etc. The content of tetrafluoroethylene units in the partially fluorinated rubber (content of polymerization units based on tetrafluoroethylene relative to the total polymerization units of the partially fluorinated rubber) may be less than 40 mol%.

[0306] Examples of partially fluorinated rubbers include tetrafluoroethylene (TFE), vinylidene fluoride (VdF), and rubbers with the general formula: CF2=CF-Rf a (In the formula, Rf a -CF3 or -ORf b (Rf b It is preferable that the partially fluorinated rubber contains monomer units based on at least one monomer selected from the group consisting of perfluoroethylenically unsaturated compounds represented by perfluoroalkyl groups having 1 to 5 carbon atoms (for example, hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), etc.). Among the partially fluorinated rubbers, it is preferable that they contain VdF units or TFE units.

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

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

[0309] Other monomers copolymerizable with the above vinylidene fluoride include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], fluoroalkyl vinyl ether, chlorotrifluoroethylene [CTFE], trifluoroethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, and general formula (100):CHX 101 =CX 102 Rf 101 (In the formula, X 101 and X 102 In this case, one side is H, the other is F, and Rf 101 Fluoromers represented by a linear or branched fluoroalkyl group having 1 to 12 carbon atoms, general formula (170): CH2=CH-(CF2) n -X 171(In the formula, X 171 A is H or F, and n is an integer from 3 to 10. Examples include fluoromonomers represented by (160), monomers that provide a crosslinking site, and non-fluorinated monomers such as ethylene, propylene, and alkyl vinyl ethers. These can be used individually 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, fluoroalkyl vinyl ether, and CTFE. As the fluoroalkyl vinyl ether, a fluoromonomer represented by general formula (160) is preferred.

[0310] Specific examples of vinylidene fluoride-based fluororubbers include VdF / HFP rubber, VdF / HFP / TFE rubber, VdF / CTFE rubber, VdF / CTFE / TFE rubber, VdF / fluoromonomer rubber represented by general formula (100), VdF / fluoromonomer / TFE rubber represented by general formula (100), VdF / perfluoro(methyl vinyl ether) [PMVE] rubber, VdF / PMVE / TFE rubber, and VdF / PMVE / TFE / HFP rubber. As the fluoromonomer rubber represented by VdF / general formula (100), VdF / CH2=CFCF3 rubber is preferred, and as the fluoromonomer / TFE rubber represented by VdF / general formula (100), VdF / TFE / CH2=CFCF3 rubber is preferred.

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

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

[0313] The above VdF / CH2=CFCF3 rubber is preferably a copolymer consisting of 40 to 99.5 mol% VdF and 30.5 to 60 mol% CH2=CFCF, and more preferably a copolymer consisting of 50 to 85 mol% VdF and 320 to 50 mol% CH2=CFCF.

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

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

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

[0317] The above-mentioned fluororubber may be a perfluororubber. The above-mentioned perfluororubber is preferably at least one selected from the group consisting of a perfluororubber containing TFE, for example, a fluoromonomer copolymer represented by general formula (160), (130), or (140) and a fluoromonomer / monomer copolymer that provides a crosslinking site represented by general formula (160), (130), or (140).

[0318] In the case of the 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 monomer copolymers that provide TFE / PMVE / crosslinking sites, the preferred values ​​are 45-89.9 / 10-54.9 / 0.01-4 (mol%), more preferably 55-77.9 / 20-49.9 / 0.1-3.5, and even more preferably 55-69.8 / 30-44.8 / 0.2-3.

[0320] In the case of a fluoromonomer copolymer represented by general formula (160), (130), or (140) with 4 to 12 carbon atoms, the ratio 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 a TFE / fluoromonomer represented by general formula (160), (130), or (140) having 4 to 12 carbon atoms / monomer copolymer that provides a crosslinking site, the preferred values ​​are 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] Outside of these compositional ranges, the rubber-elastic properties are lost, and the material tends to become closer in properties to that of a resin.

[0323] The perfluororubber described above is preferably at least one selected from the group consisting of TFE / fluoromonomer represented by general formula (140) / fluoromonomer copolymers that provide crosslinking sites, TFE / perfluorovinyl ether copolymers represented by general formula (140), fluoromonomer copolymers represented by general formula (160), and fluoromonomer / monomer copolymers that provide crosslinking sites represented by general formula (160).

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

[0325] The above-mentioned fluororubber is preferably such that its glass transition temperature is -70°C or higher, more preferably -60°C or higher, and even more preferably -50°C or higher, in order to have excellent compression set resistance at high temperatures. Furthermore, in order to have good cold resistance, it is preferably such that its glass transition temperature is 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 using a differential scanning calorimeter (Mettler-Toledo, DSC822e) to obtain a DSC curve by heating 10 mg of the sample at 10°C / min, and finding the point where the maximum value is obtained in the differential curve of the DSC curve during the second-order transition.

[0327] The above-mentioned fluororubber has good heat resistance, and preferably has a Mooney viscosity ML(1+20) of 30 or higher at 170°C, more preferably 40 or higher, and even more preferably 50 or higher. Furthermore, in terms of good processability, it has a viscosity of 150 or lower, more preferably 120 or lower, and even more preferably 110 or lower.

[0328] The above-mentioned fluororubber has good heat resistance, and preferably has a Mooney viscosity ML(1+20) of 30 or higher at 140°C, more preferably 40 or higher, and even more preferably 50 or higher. Furthermore, in terms of good processability, it has a viscosity of 180 or lower, more preferably 150 or lower, and even more preferably 110 or lower.

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

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

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

[0332] Examples of the curing agents mentioned above include polyols, polyamines, organic peroxides, organotin compounds, bis(aminophenol)tetraamine, or bis(thioaminophenol).

[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 agent. Examples of molding methods include compression molding, injection molding, injection molding, extrusion molding, and molding by funnel curing, but are not limited to these.

[0334] When a 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). Crosslinking methods include steam crosslinking, heating crosslinking, and radiation crosslinking, with steam crosslinking and heating crosslinking being preferred. Specific crosslinking conditions, though not limited to these, are typically within a temperature range of 140-250°C and a crosslinking time of 1 minute to 24 hours, which can be appropriately determined depending on the type of crosslinking accelerator, crosslinking agent, and acid acceptor.

[0335] The above-mentioned fluororubber molded articles are suitable for use as seals, gaskets, wire insulation, hoses, tubes, laminates, accessories, etc., and are particularly suitable for use as parts for semiconductor manufacturing equipment, automotive parts, etc.

[0336] The polymerization described above preferably involves polymerizing fluoromonomers in the absence of substantially fluorine-containing surfactants (excluding compounds having functional groups and hydrophilic groups that can react by radical polymerization). Conventionally, fluorine-containing surfactants have been used for the polymerization of fluoromonomers in aqueous media, but according to the manufacturing method of this disclosure, fluororubber can be obtained even without using fluorine-containing surfactants.

[0337] In this disclosure, "substantially in the absence of fluorine-containing surfactants" means that the amount of fluorine-containing surfactant in the aqueous medium is 10 ppm by mass or less. The amount of fluorine-containing surfactant in 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.

[0338] Examples of fluorine-containing surfactants include anionic fluorine-containing surfactants. The above-mentioned anionic fluorine-containing surfactant may be, for example, a surfactant containing fluorine atoms with a total number of carbon atoms of 20 or less in the part excluding the anionic group.

[0339] The above-mentioned fluorine-containing surfactant may also be a surfactant containing fluorine with a molecular weight of 1000 or less in the anionic portion. The above-mentioned "anionic portion" refers to the portion of the fluorine-containing surfactant excluding the cation. For example, F(CF2) represented by formula (I) described later. n1 In the case of COOM, "F(CF2)" n1 This is the "COO" part.

[0340] The above-mentioned fluorine-containing surfactants also include fluorine-containing surfactants with a LogPOW of 3.5 or less. The above LogPOW is the partition coefficient between 1-octanol and water, and is expressed as LogP [wherein P represents the ratio of the concentration of the fluorine-containing surfactant in octanol to the concentration of the fluorine-containing surfactant in water when a 1:1 mixture of octanol and water containing the fluorine-containing surfactant undergoes phase separation]. The above LogPOW is calculated by performing HPLC on standard substances with known octanol / water partition coefficients (heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid) under the following conditions: column; TOSOH ODS-120T column (φ4.6 mm × 250 mm, manufactured by Tosoh Corporation), eluent; acetonitrile / 0.6 mass% HClO4 water = 1 / 1 (vol / vol%), flow rate; 1.0 ml / min, sample volume; 300 μL, column temperature; 40°C, detection light; UV 210 nm. A calibration curve is created between the elution time and the known octanol / water partition coefficient, and the LogPOW is calculated from the elution time of the sample solution using this calibration curve.

[0341] Specifically, the above-mentioned fluorine-containing surfactants include U.S. Patent Publication No. 2007 / 0015864, U.S. Patent Publication No. 2007 / 0015865, U.S. Patent Publication No. 2007 / 0015866, U.S. Patent Publication No. 2007 / 0276103, U.S. Patent Publication No. 2007 / 0117914, U.S. Patent Publication No. 2007 / 142541, U.S. Patent Publication No. 2008 / 0015319, and U.S. Patent No. 3250808. Examples include those described in the book, U.S. Patent No. 3,271,341, Japanese Patent Publication No. 2003-119204, International Publication No. 2005 / 042593, International Publication No. 2008 / 060461, International Publication No. 2007 / 046377, Japanese Patent Publication No. 2007-119526, International Publication No. 2007 / 046482, International Publication No. 2007 / 046345, U.S. Patent Application Publication No. 2014 / 0228531, International Publication No. 2013 / 189824, and International Publication No. 2013 / 189826.

[0342] The above anionic fluorine-containing surfactants include those with the following general formula (N 0 ): X n0 -Rf n0 -Y 0 (N 0 ) (In the formula, X n0 Rf is H, Cl, or F. n0 This is an alkylene group having 3 to 20 carbon atoms, being linear, branched, or cyclic, in which some or all of the hydrogen atoms are substituted with fluorine, and the alkylene group may contain one or more ether bonds, and some of the hydrogen atoms may be substituted with chlorine. 0 The group is an anionic group. Examples of compounds represented by ) are shown. Y 0 The anionic group may be -COOM, -SO2M, or -SO3M. M is H, a metal atom, NR 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7is either H or an organic group. Examples of the above-mentioned metal atoms include alkali metals (Group 1) and alkaline earth metals (Group 2), such as Na, K, or Li. R 7 For example, H or C 1-10 The organic group may be H or C 1-4 The organic group may be H or C 1-4 It may be an alkyl group. M is H, a metal atom, or NR 7 It may be 4, and may be H, alkali metals (Group 1), alkaline earth metals (Group 2), or NR 7 It may be 4, and may be H, Na, K, Li, or NH4. The above Rf n0 It is acceptable if 50% or more of the H atoms are replaced with fluorine.

[0343] The above general formula (N 0 Compounds represented by ) include: The following general formula (N 1 ): X n0 -(CF2) m1 -Y 0 (N 1 ) (In the formula, X n0 These are H, Cl, and F, and m1 is an integer from 3 to 15, Y 0 This is defined above. ) A compound represented by the following general formula (N 2 ): Rf n1 -O-(CF(CF3)CF2O) m2 CFX n1 -Y 0 (N 2 ) (In the formula, Rf n1 m2 is a perfluoroalkyl group having 1 to 5 carbon atoms, m2 is an integer from 0 to 3, and X n1 is F or CF3, and Y 0 This is defined above. ) A compound represented by the following general formula (N 3 ): Rf n2 (CH2) m3 -(Rfn3 ) q -Y 0 (N 3 ) (In the formula, Rf n2 m3 is a partially or fully fluorinated alkyl group that may contain ether bonds between 1 and 13 carbon atoms, and m3 is an integer between 1 and 3, and Rf n3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, where q is 0 or 1, and Y 0 This is defined above. ) A compound represented by the following general formula (N 4 ): Rf n4 -O-(CY n1 Y n2 ) p CF2-Y 0 (N 4 ) (In the formula, Rf n4 Y is a linear or branched portion that may contain ether bonds and / or chlorine atoms with 1 to 12 carbon atoms, or a fully fluorinated alkyl group. n1 and Y n2 is the same or different, H or F, p is 0 or 1, Y 0 This refers to the compounds represented by the above definition, and the general formula (N 5 ): [ka] (In the formula, X n2 , X n3 and X n4 Rf is a linear or branched portion that may contain H, F, or an ether bond having 1 to 6 carbon atoms, or a fully fluorinated alkyl group, and may be the same or different. n5 L is a linear or branched moiety or a fully fluorinated alkylene group that may contain ether bonds with 1 to 3 carbon atoms, L is a linking group, and Y 0 This is defined above. However, X n2 , X n3 , X n4 and Rf n5 The total number of carbon atoms is 18 or less. Examples of compounds represented by ) are shown.

[0344] The above general formula (N 0 More specifically, examples of compounds represented by the formula (XII) include perfluorocarboxylic acid (I) represented by the following general formula (I), ω-H perfluorocarboxylic acid (II) represented by the following general formula (II), perfluoroether carboxylic acid (III) represented by the following general formula (III), perfluoroalkylalkylene carboxylic acid (IV) represented by the following general formula (IV), perfluoroalkoxyfluorocarboxylic acid (V) represented by the following general formula (V), perfluoroalkyl sulfonic acid (VI) represented by the following general formula (VII), ω-H perfluorosulfonic acid (VII) represented by the following general formula (VII), perfluoroalkylalkylene sulfonic acid (VIII) represented by the following general formula (VIII), alkylalkylene carboxylic acid (IX) represented by the following general formula (IX), fluorocarboxylic acid (X) represented by the following general formula (X), alkoxyfluorosulfonic acid (XI) represented by the following general formula (XI), compound (XII) represented by the following general formula (XII), compound (XIII) represented by the following general formula (XIII), and so on.

[0345] The above perfluorocarboxylic acid (I) is given by the following general formula (I) F(CF2) n1 COOM (I) (In the formula, n1 is an integer between 3 and 14, and M is H, a metal atom, NR) 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (where is H or an organic group.)

[0346] The above ω-H perfluorocarboxylic acid (II) is given by the following general formula (II) H(CF2) n2 COOM (II) (In the formula, n² is an integer between 4 and 15, and M is as defined above.)

[0347] The above perfluoroether carboxylic acid (III) is given by the following general formula (III) Rf 1 -O-(CF(CF3)CF2O) n3 CF(CF3)COOM (III) (In the formula, Rf 1 (where n3 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer from 0 to 3, and M is as defined above.)

[0348] The above perfluoroalkylalkylene carboxylic acid (IV) is the following general formula (IV) Rf 2 (CH2) n4 Rf 3 COOM (IV) (In the formula, Rf 2 Rf is a perfluoroalkyl group having 1 to 5 carbon atoms. 3 (where n4 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is an integer from 1 to 3, and M is as defined above.)

[0349] The above alkoxyfluorocarboxylic acid (V) is given by the following general formula (V) Rf 4 -O-CY 1 Y 2 CF2-COOM (V) (In the formula, Rf 4 Y is a linear or branched portion that may contain ether bonds and / or chlorine atoms with 1 to 12 carbon atoms, or a fully fluorinated alkyl group. 1 and Y 2 ) are the same or different, and are represented by H or F, and M is as defined above.

[0350] The above perfluoroalkyl sulfonic acid (VI) is the following general formula (VI) F(CF2) n5 SO3M (VI) (In the formula, n5 is an integer between 3 and 14, and M is as defined above.)

[0351] The above ω-H perfluorosulfonic acid (VII) is given by the following general formula (VII) H(CF2) n6 SO3M (VII) (In the formula, n6 is an integer between 4 and 14, and M is as defined above.)

[0352] The above perfluoroalkylalkylene sulfonic acid (VIII) is given by the following general formula (VIII) Rf 5 (CH2) n7 SO3M (VIII) (In the formula, Rf 5 (where n7 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer from 1 to 3, and M is as defined above.)

[0353] The above alkylalkylene carboxylic acid (IX) is the following general formula (IX) Rf 6 (CH2) n8 COOM (IX) (In the formula, Rf 6 (where n8 is a linear or branched portion that may contain ether bonds with 1 to 13 carbon atoms, or a fully fluorinated alkyl group, n8 is an integer from 1 to 3, and M is as defined above.)

[0354] The above fluorocarboxylic acid (X) is given by the following general formula (X) Rf 7 -O-Rf 8 -O-CF2-COOM (X) (In the formula, Rf 7 Rf is a linear or branched moiety or a fully fluorinated alkyl group that may contain ether bonds and / or chlorine atoms with 1 to 6 carbon atoms. 8 (where M is a linear or branched portion having 1 to 6 carbon atoms or a fully fluorinated alkyl group, and M is as defined above.)

[0355] The above alkoxyfluorosulfonic acid (XI) is given by the following general formula (XI) Rf 9 -O-CY 1 Y 2 CF2-SO3M (XI) (In the formula, Rf 9 Y is a partially or fully fluorinated alkyl group that may contain ether bonds between 1 to 12 carbon atoms, and may contain chlorine. 1 and Y 2 ) are the same or different, and are represented by H or F, and M is as defined above.

[0356] The above compound (XII) has the following general formula (XII): [ka] (In the formula, X 1 , X 2 and X 3 Rf is a linear or branched portion that may contain H, F and ether bonds having 1 to 6 carbon atoms, or a fully fluorinated alkyl group, and may be the same or different. 10 L is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, and Y 0 It is an anionic group. ) Y 0 may be -COOM, -SO2M, or -SO3M, or -SO3M, or COOM (wherein M is as defined above). Examples of L include single bonds, moieties that may contain ether bonds with 1 to 10 carbon atoms, or fully fluorinated alkylene groups.

[0357] The above compound (XIII) has the following general formula (XIII): Rf 11 -O-(CF2CF(CF3)O) n9 (CF2O) n10 CF2COOM (XIII) (In the formula, Rf 11This is represented as follows: is a fluoroalkyl group having 1 to 5 carbon atoms and containing chlorine, n9 is an integer from 0 to 3, n10 is an integer from 0 to 3, and M is as defined above. Compound (XIII) is CF2ClO(CF2CF(CF3)O) n9 (CF2O) n10 One example is CF2COONH4 (a mixture with an average molecular weight of 750, where n9 and n10 are as defined above).

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

[0359] The fluorine-containing surfactant may be a single fluorine-containing surfactant or a mixture containing two or more fluorine-containing surfactants.

[0360] Examples of fluorine-containing surfactants include compounds represented by the following formula. The fluorine-containing surfactant may be a mixture of these compounds. In one embodiment of the polymerization described above, the fluoromonomer is polymerized in substantially the absence of the compound represented by the following formula. F(CF2)7COOM, F(CF2)5COOM, H(CF2)6COOM, H(CF2)7COOM, CF3O(CF2)3OCHFCF2COOM, CF3(CF2)5CH2CH2SO3M, C3F7OCF(CF3)CF2OCF(CF3)COOM, CF3CF2CF2OCF(CF3)COOM, CF3CF2OCF2CF2OCF2COOM, C2F5OCF(CF3)CF2OCF(CF3)COOM, CF3OCF(CF3)CF2OCF(CF3)COOM, CF2ClCF2CF2OCF(CF3)CF2OCF2COOM, CF2ClCF2CF2OCF2CF(CF3)OCF2COOM, CF2ClCF(CF3)OCF(CF3)CF2OCF2COOM, CF2ClCF(CF3)OCF2CF(CF3)OCF2COOM, [ka] (In each formula, M is H, metal atom, NR 7 4. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 (This is either H or an organic group.)

[0361] (aqueous medium) In the method for producing the composition, the aqueous medium 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 with a boiling point of 40°C or lower.

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

[0363] The fluororubber content in the polymerization dispersion is obtained by drying 1 g of the polymerization dispersion in a forced-air dryer at 150°C for 60 minutes, measuring the mass of the residue after heating, and calculating the ratio of the mass of the residue to the mass of the polymerization dispersion (1 g) as a percentage.

[0364] (Form of composition and other components) The form of the composition of this disclosure is not particularly limited, but may be gum, crumb, powder, pellets, etc., and gum or crumb is preferred. 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 gum at room temperature and fuses with each other. Gum or crumb is preferably obtained by drying a coagulation product obtained by coagulation.

[0365] One embodiment of the composition of this disclosure contains a fluorine-containing surfactant. Compositions containing a fluorine-containing surfactant have the advantage of being able to be manufactured stably with high productivity using the fluorine-containing surfactant.

[0366] One embodiment of the composition of this disclosure is substantially free of fluorine-containing surfactants. Compositions substantially free of fluorine-containing surfactants typically require polymerization of fluoromonomers without the use of fluorine-containing surfactants, but this is made possible by the manufacturing method of this disclosure using polymer (I).

[0367] In this disclosure, "substantially free of fluorine-containing surfactants" means that the content of fluorine-containing surfactants 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 1 ppb by mass or less, and particularly preferably the amount of fluorine-containing surfactants is below the detection limit as measured by liquid chromatography-mass spectrometry (LC / MS).

[0368] The content of fluorine-containing surfactants can be quantified by known methods. For example, it can be quantified by LC / MS analysis. First, methanol is added to the composition, and extraction is performed. The resulting extract is then analyzed by LC / MS. To further improve extraction efficiency, treatments such as Soxhlet extraction or sonication may be performed. From the obtained LC / MS spectrum, molecular weight information is extracted and its agreement with the structural formula of the candidate fluorine-containing surfactant is confirmed. Subsequently, aqueous solutions containing five or more levels of the identified fluorine-containing surfactant were prepared, and LC / MS analysis was performed on each aqueous solution with its respective content. The relationship between the content and the area area corresponding to that content was plotted, and a calibration curve was drawn. Furthermore, using a calibration curve, the area of ​​the LC / MS chromatogram for fluorine-containing surfactants in the extract can be converted to the content of fluorine-containing surfactants.

[0369] (Method of manufacturing the composition) As described above, the compositions of this disclosure can be produced by polymerizing fluoromonomers in an aqueous medium in the presence of polymer (I) to obtain a polymerization dispersion containing fluororubber, and then performing one of the following treatments on the obtained polymerization dispersion. In this production method, fluororubber can be coagulated without using a coagulant containing inorganic acids or metal elements. (1) The fluororubber in the polymerization dispersion is brought into contact with an alcohol having 3 to 6 carbon atoms per OH group to cause the fluororubber to coagulate. (2) The polymerization dispersion is frozen to cause the fluororubber to coagulate. (3) The fluororubber in the polymerization dispersion is brought into contact with a very limited type of organic solvent to cause the fluororubber to coagulate.

[0370] By polymerizing fluoromonomers 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 the aqueous medium is usually obtained. Subsequently, the fluororubber can be recovered from the polymerization dispersion by coagulating the fluororubber particles. Next, the coagulation methods (1) to (3) will be described in more detail.

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

[0372] The alcohol may be a monohydric alcohol, a dihydric alcohol, or a trihydric alcohol. A monohydric alcohol is preferred because it further improves the removal efficiency of 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, and is preferably 4 or more, and preferably 5 or less, as this further improves the removal efficiency of polymer (I).

[0374] As for alcohol, for example, Alcohols with 3 carbon atoms per OH group, such as 1-propanol and 2-propanol. Alcohols with 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 with 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 with 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; These are some examples.

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

[0376] As for the alcohol, an alcohol with a MolLogP in the range of 0.3 to 1.6 is preferred, as it further improves the removal efficiency of polymer (I). More preferably, the MolLogP is 1.2 or less.

[0377] Examples of alcohols with 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] As for the alcohol, at least one selected from the group consisting of 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol is preferred.

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

[0381] The method for bringing the fluororubber in the polymerization dispersion into contact with the alcohol is not particularly limited and includes methods such as adding the polymerization dispersion to the alcohol or adding the alcohol to the polymerization dispersion. The mixture containing the polymerization dispersion and the alcohol may be stirred to bring the fluororubber into sufficient contact with the alcohol and cause the fluororubber in the polymerization dispersion to coagulate. Furthermore, the coagulation of the fluororubber may be carried out in a batch process or a continuous process.

[0382] As a method for bringing fluororubber in a polymerization dispersion into contact with alcohol, it is preferable to drop or add the polymerization dispersion obtained by polymerization to alcohol or an alcohol-containing composition, as this further improves the efficiency of removing polymer (I).

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

[0384] The amount of alcohol used for coagulation is preferably 0.5 times or more the weight (dry weight) of the fluororubber in the polymerization dispersion used for coagulation, as this further improves the efficiency of polymer (I) removal. More preferably, the amount of alcohol used for coagulation is 1.0 times or more, and even more preferably 1.5 times or more. If the amount of alcohol is too little, coagulation will be incomplete, which may lead to problems such as polymer loss and equipment blockage. There is no particular upper limit to the amount of alcohol, but for reasons such as economy and equipment 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 diluted with water as appropriate. In one embodiment, the fluororubber is contacted with the alcohol using a polymerization dispersion in which the fluororubber concentration obtained by polymerization is 20-40% relative to water. In another embodiment, the polymerization dispersion obtained by polymerization is diluted with water, and the fluororubber is contacted with the alcohol using a 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, with the polymerization dispersion being considered as 1x. If the dilution ratio is too high, coagulation tends to be incomplete, and if the dilution ratio is too low, the number of washing cycles tends to increase. In addition, the alcohol may be diluted with water before contacting the fluororubber in the polymerization dispersion with the alcohol.

[0386] The temperatures at which the fluororubber and alcohol in the polymerization dispersion are brought into contact are 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, as this further improves the efficiency of polymer (I) removal.

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

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

[0389] When coagulation is performed by contacting fluororubber in a polymerization dispersion with alcohol, polymer (I) is removed from the resulting coagulate. However, it is preferable to further wash the resulting coagulate in order to further improve the efficiency of polymer (I) removal.

[0390] By using the coagulation method (1) to coagulate fluororubber and washing the resulting coagulation with water under appropriate conditions, a composition with an even lower polymer (I) content can be obtained. By washing the coagulation with water under appropriate conditions, for example, the polymer (I) content 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, relative to the fluororubber.

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

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

[0393] The coagulated material can be washed once or two or more times. The washing method is not particularly limited, but for example, it can be carried out by putting the coagulated material and water into a washing tank and stirring. If washing is performed two or more times, it can be carried out by repeating the process of putting the coagulated material and water into a washing tank, stirring, and dewatering. The number of times the coagulated material is washed is preferably two or more times, more preferably three or more times, preferably 10 or less, and more preferably 6 or less.

[0394] After coagulation or washing of the fluororubber, the fluororubber can be dried.

[0395] (Coagulation method (2)) (2) The polymerization dispersion is frozen to cause the fluororubber to coagulate.

[0396] Fluororubber can be coagulated by freezing the polymerization dispersion and then thawing the frozen polymerization dispersion. Furthermore, in order to reduce the polymer (I) content in the fluororubber, a small amount of alcohol that can be used in coagulation method (1) or an organic solvent that can be used in coagulation method (3) may be added to the polymerization dispersion as an auxiliary agent, in an amount that does not cause the polymerization dispersion to coagulate, and after mixing, freeze-coagulation may be performed.

[0397] The freezing temperature of the polymerization dispersion is not particularly limited and may be below the freezing temperature of the polymerization dispersion. The freezing temperature is preferably 0 to -196°C, more preferably -5°C to -50°C, and more preferably -10°C to -30°C or higher. If the freezing temperature is too high, coagulation may be insufficient, and if it is too low, excessive energy may be required, which may be economically disadvantageous.

[0398] The temperature at which the frozen polymerization dispersion is melted is not particularly limited and may be above the melting temperature of the polymerization dispersion and below 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 performed by freezing the polymerization dispersion, polymer(I) is removed from the resulting precipitate. However, it is preferable to further wash the obtained precipitate in order to further improve the efficiency of polymer(I) removal.

[0400] After coagulation or washing of the fluororubber, the fluororubber can be dried.

[0401] (Coagulation method (3)) (3) The fluororubber in the polymerization dispersion is brought into contact with a very limited type of organic solvent to cause the fluororubber to coagulate.

[0402] As an organic solvent, at least one selected from the group consisting of the following compounds can be used. 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

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

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

[0405] The method for bringing the fluororubber into contact with the organic solvent is not particularly limited and includes methods such as adding the polymerization dispersion to the organic solvent or adding the organic solvent to the polymerization dispersion. The mixture containing the polymerization dispersion and the organic solvent may be stirred to bring the fluororubber into sufficient contact with the organic solvent and cause the fluororubber in the polymerization dispersion to coagulate. Furthermore, the coagulation of the fluororubber may be carried out in a batch process or a continuous process.

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

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

[0408] The amount of organic solvent used for coagulation is preferably 0.5 times or more the weight (dry weight) of fluororubber in the polymerization dispersion used for coagulation, in order to further improve the efficiency of polymer (I) removal. More preferably, the amount of organic solvent used for coagulation is 1.0 times or more, and even more preferably 1.5 times or more. If the amount of organic solvent is too little, coagulation will be incomplete, which may lead to problems such as polymer loss and equipment blockage. There is no particular upper limit to the amount of organic solvent, but for reasons such as economy and equipment capacity, it is preferably 40 times or less, more preferably 10 times or less, and even 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 diluted with water as appropriate. In one embodiment, the polymerization dispersion obtained by polymerization, with a fluororubber concentration of 20-40% relative to water, is used to contact the fluororubber with the organic solvent. In another embodiment, the polymerization dispersion obtained by polymerization is diluted with water, and the polymerization dispersion with the adjusted fluororubber concentration is used to contact the fluororubber with the organic solvent. The dilution ratio is preferably 1 to 10 times, more preferably 1 to 6 times, and even more preferably 1.5 to 4 times, with the polymerization dispersion being considered as 1 time. If the dilution ratio is too high, coagulation tends to be incomplete, and if the dilution ratio is too low, the number of washing cycles tends to increase. In addition, the organic solvent may be diluted with water before contacting the fluororubber in the polymerization dispersion with the organic solvent.

[0410] The temperatures at which the fluororubber in the polymerization dispersion is brought into contact with the organic solvent are 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, as this further improves the efficiency of polymer (I) removal.

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

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

[0413] When coagulation is performed by contacting fluororubber in a polymerization dispersion with an organic solvent, polymer (I) is removed from the resulting coagulated product. However, it is preferable to further wash the resulting coagulated product in order to further improve the efficiency of polymer (I) removal.

[0414] After coagulation or washing of the fluororubber, the fluororubber can be dried.

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

[0416] The crosslinkable composition of this disclosure contains the above-described composition, as well as at least one selected from the group consisting of inorganic nitrides, organotin compounds, ammonia-generating compounds, and crosslinking agents. A crosslinked product can be obtained by crosslinking the crosslinkable composition of this disclosure.

[0417] Inorganic nitrides are not particularly limited, but examples include silicon nitride (Si3N4), lithium nitride, titanium nitride, aluminum nitride, boron nitride, vanadium nitride, and zirconium nitride. Among these, silicon nitride is preferred because nano-sized particles can be supplied.

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

[0419] As for compounds that generate ammonia, compounds that generate ammonia at 40 to 330°C are preferred.

[0420] The ammonia-generating compound is preferably urea or its derivatives or ammonium salts, more preferably urea or ammonium salts, and even more preferably urea. The ammonium salt may be either an organic or inorganic ammonium salt. Furthermore, the ammonia-generating compound may be one that reacts with a small 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 Japanese Patent Publication No. 9-111081, International Publication No. 00 / 09603, and International Publication No. 98 / 23675, such as ammonium salts of polyfluorocarboxylic acids like ammonium perfluorohexanoate and ammonium perfluorooctanoate; ammonium salts of polyfluorosulfonic acids like ammonium perfluorohexanesulfonate and ammonium perfluorooctanesulfonate; ammonium salts of polyfluoroalkyl group-containing phosphoric acid or phosphonic acid like ammonium perfluorohexanephosphate and ammonium perfluorooctanesulfonate; and ammonium salts of non-fluorinated carboxylic acids or sulfonic acids like ammonium benzoate, ammonium adipate, and ammonium phthalate.

[0423] Examples of inorganic ammonium salts include compounds described in Japanese Patent Publication No. 9-111081, such as ammonium sulfate, ammonium carbonate, ammonium nitrate, and ammonium phosphate.

[0424] Other ammonia-generating compounds include acetaldehyde ammonia, hexamethylenetetramine, formamidine, formamidine hydrochloride, formamidine acetate, t-butylcarbamate, benzylcarbamate, HCF2CF2CH(CH3)OCONH2, and phthalamide.

[0425] Examples of crosslinking agents include those 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 can be any organic peroxide that can readily generate peroxy radicals in the presence of heat or an oxidation-reduction system. Specifically, examples include 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butylperoxide (perbutyl D), t-butylcumylperoxide (perbutyl C), dicumylperoxide (permyl D, permyl D-40, permyl D-40MB(T)), α,α- Bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (perhexa25B, perhexa25B-40), 2,5-dimethyl-2,5-di(t-butylperoxy)-hexyn-3 (perhexyn25B, perhexyn25B-40), benzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane (perhexa25Z), t-butylperoxymaleic acid (t-butylMA), t-butyl Tyl peroxyisopropyl 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-hexyl peroxy)-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)butyl pentanoate (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 (Permil P), 1,1,3,3-tetramethylbutyl hydroperoxide (Perocta H), cumene hydroperoxide (Permil H-80), t-butyl hydroperoxide (Perbutyl H-69), di(2-t-butylperoxyisopropyl) Perfumes (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), Disuccinate peroxide (Perloyl SA), Di-(3-methylbenzoyl) Peroxide, benzoyl (3-methylbenzoyl) peroxide, and mixtures of dibenzoyl peroxide (Nipper BMT-K40, Nipper BMT-M), dibenzoyl peroxide (Nipper BW, Nipper BO, Nipper FF, Nipper BS, Nipper E, Nipper NS), di(4-methylbenzoyl) peroxide (Nipper PMB), di-n-propyl peroxydicarbonate (Perloyl 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 (perloyl ND, perloyl 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-tetramethylbutyl peroxy-2-ethylhexanoate (Perocta O), 2,5-dimethyl-2,5-di(2-ethylhexanoyl peroxy)hexane (Perhexa 25 O), t-hexyl peroxy-2-ethylhexanoate (Perhexyl O, Percure HO(N)), t-butyl peroxy-2-ethylhexanoate (Perb Chill O, Percure O), t-hexyl peroxyisopropyl monocarbonate (Perhexyl I), t-butyl peroxy-3,5,5-trimethylhexanoate (Perbutyl 355), t-butyl peroxylaurate (Perbutyl L), t-butyl peroxy-2-ethylhexyl monocarbonate (Perbutyl E), t-hexyl peroxybenzoate (Perhexyl Z), t-butyl peroxyacetate (Perbutyl A), Examples include t-butylperoxy-3-methylbenzoate and a mixture of t-butylperoxybenzoate (Perbutyl ZT), t-butylperoxybenzoate (Perbutyl Z), t-butylperoxyallyl monocarbonate (Peromer AC), 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone (BTTB-25), and 2,3-dimethyl-2,3-diphenylbutane (Nofmer BC-90). Among these, dialkyl types are preferred. Furthermore, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane is particularly preferred. Generally, the type and amount of organic peroxide used are selected considering the amount of active -OO-, decomposition temperature, etc.

[0427] Furthermore, any crosslinking aid that can be used in this case is a compound that has reactive activity toward peroxy radicals and polymer radicals, and examples include polyfunctional compounds having functional groups such as -CH=CH2, -CH2CH=CH2, -CF=CF2, -C(CF3)=CF2, -C(CH3)=CF2, -CF=CF(CF3), -CF=CF(CH3), -C(C6H5)=CF2, -CF=CF(C6H5), -CH=CF2, -CF=CHF, -C(CF3)=CHF, -CF=CH(CF3), and -CH=CF(CF3) (where "C6H5" represents a phenyl group). Specifically, examples include triallyl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N,N'-n-phenylene bismaleimide, dipropagyl 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-diallylcrylamide, and 1,6-divindodecafluorohexane.

[0428] Furthermore, as a crosslinking aid used together with the peroxide crosslinking agent, the general formula (31): [ka] (In the formula, there are six R 31 Each of these is an independently selected halogenated group having 1 to 5 carbon atoms, which may contain H, a halogen atom, or an ether bond, and Z 31 This can 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.

[0429] Compounds represented by general formula (31) include general formula (32): [ka] (In the formula, j is an integer from 2 to 10, preferably an integer from 4 to 8, and four R 32 Each of these is independently a compound represented by H, F, or an alkyl group or (per)fluoroalkyl group having 1 to 5 carbon atoms, general formula (33): [ka] (In the formula, Y 31 These are F, Cl, or H, respectively, and Y 32 These are F, Cl, H, or OR, each independently. 33 (Here, R 33 (which may be partially, substantially, or completely fluorinated or chlorinated, and is a branched or linear alkyl group) 33 This is a divalent group having 2 to 10 carbon atoms, optionally fluorinated, which may have an ether bond inserted, preferably Z 33 This is -(CF2) where m is an integer between 3 and 5. m - Compounds that are a group and represented by general formula (33) are preferably compounds represented by F2C=CF-O-(CF2)5-O-CF=CF2, general formula (34): [ka] (In the formula, Y 31 , Y 32 and Z 33 As stated above, R 34 Examples of compounds that can be independently represented by H, F, or an alkyl group or (per)fluoroalkyl group having 1 to 5 carbon atoms.

[0430] Crosslinking agents, or crosslinking aids used with peroxide crosslinking agents, include general formula (35): [ka]

[0431] (In the formula, R 35 ~R 37 Each of these is independently a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, or a substituted or unsubstituted aryl group, R 35 ~R 37 At least one of them is a fluorine atom or a group containing a fluorine atom. m is an integer from 1 to 5. If m is 2 or greater, there are m R 35 ~R 37 These may be the same or different. The hydrogen atoms of the benzene ring may be substituted. We can also list compounds having at least one structure represented by ). When m is 1, it is preferable to have two or more of these structures.

[0432] Compounds having a structure represented by general formula (35) include general formula (36): [ka]

[0433] (In the formula, R 35 ~R 37 As stated above, p is an integer between 0 and 2, and n is an integer between 2 and 6. The compound represented by the general formula (37): [ka]

[0434] (In the formula, R 35 ~R 37 As stated above. R 38 m is a single bond, -SO2-, -O-, -S-, -CO-, heteroatom-containing group, substituted or unsubstituted alkylene group, substituted or unsubstituted cycloalkylene group, or substituted or unsubstituted arylene group. m is an integer from 1 to 5. Some or all of these groups may be fluorinated. Examples include compounds represented by ().

[0435] The heteroatom-containing group is not particularly limited as long as it is a divalent group containing a heteroatom. Examples of heteroatoms include oxygen, nitrogen, sulfur, boron, and phosphorus atoms.

[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 polyhydric amine compounds such as hexamethylenediamine carbamate, N,N'-disinnamyridene-1,6-hexanediamine, and 4,4'-bis(aminocyclohexyl)methanecarbamate.

[0438] Examples of crosslinking agents used in triazine crosslinking include organotin compounds such as tetraphenyltin and triphenyltin.

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

[0440] [ka]

[0441] (In the formula, R 41 -SO2-, -O-, -CO-, alkylene groups with 1 to 6 carbon atoms, perfluoroalkylene groups with 1 to 10 carbon atoms, or single bonds,

[0442] [ka]

[0443] The group is represented by R 42 and R 43 One side is -NH2 and the other is -NHR 44 , -NH2, -OH or -SH, R 44 is a hydrogen atom, a fluorine atom, or a monovalent organic group, preferably R42 is -NH2 and R 43 ga-NHR 44 Preferred specific examples of alkylene groups having 1 to 6 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, and hexylene groups, while perfluoroalkylene groups having 1 to 10 carbon atoms include,

[0444] [ka]

[0445] These include the following. Note that these compounds are known as examples of bisdiaminophenyl compounds in Japanese Patent Publication No. 2-59177, Japanese Patent Publication No. 8-120146, etc.) Bisdiaminophenyl crosslinking agents, bisaminophenol crosslinking agents, bisaminothiophenol crosslinking agents, general formula (42):

[0446] [ka] (R 41 As mentioned above, R 45 Each of these is independently one of the following bases. [ka]

[0447] A bisamido-razone crosslinking agent represented by general formula (43):

[0448] [ka]

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

[0450] [ka]

[0451] Bisamido oxime crosslinking agents represented by the formula (where n is an integer from 1 to 10), general formula (45): HN=CR 45 R 46 (In the formula, R 45 These are H, NH2, and NHR 47 Selected from the group consisting of R 46 Ph, SO2H, NR 48 R 49 Selected from the group consisting of , 2-pyridine, and CH2CONH2, R 47 It is selected from the group consisting of Ph, NH2, and CN, and R 48 is selected from the group consisting of H, NHPh, CH2CONH2, linear alkyl groups having 1 to 8 carbon atoms, and branched alkyl groups having 1 to 8 carbon atoms, and R 49 Ph, COOC(CH3)3, NH2, CH2COOH, CSNH2, CNHNH3 + Cl - p-phenylCN, [ka] Examples include compounds represented by (selected from the group consisting of COPh). These bisaminophenol crosslinking agents, bisaminothiophenol crosslinking agents, or bisdiaminophenyl crosslinking agents have conventionally been used in crosslinking systems with cyano groups as crosslinking sites, but they also react with carboxyl groups and alkoxycarbonyl groups to form oxazole rings, thiazole rings, and imidazole rings, giving crosslinked products.

[0452] Furthermore, as a crosslinking agent, the general formula (46):X 41 -(CH2) n -R 50 -(CH2) m -X 41 (In the formula, X 41 These are, independently, an alkyne group, a cyano group, or Y 41 P N3(Y 41(where is SO, SO2, C6H4 or CO, and p is 0 or 1), n ​​and m are independent integers from 1 to 4, and R 50 teeth, i) Fluoroalkylene group having 3 to 10 carbon atoms, ii) Fluoroalkoxylene groups having 3 to 10 carbon atoms, iii) Substituted arylene group, iv) Oligomers containing copolymer units of vinylidene fluoride and perfluoro(methyl vinyl ether), v) Oligomers containing copolymer units of vinylidene fluoride and hexafluoropropylene, vi) Oligomers containing copolymer units of tetrafluoroethylene and perfluoro(methyl vinyl ether), and vii) A crosslinking agent may also be cited, which is selected from the group consisting of oligomers containing copolymer units of tetrafluoroethylene and hydrocarbon olefins. This crosslinking agent is preferably used 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 and give a crosslinked product.

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

[0454] [ka]

[0455] (In the formula, R 41 , R 42 and R 43Examples of compounds represented as above include, specifically, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (generic 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)pheni Examples include 2,2-bis[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, and 2,2-bis[3-amino-4-(N-benzylamino)phenyl]hexafluoropropane.

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

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

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

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

[0460] The content of polymer (I) in the crosslinkable composition of this disclosure is preferably 0.0001 to 1.0% by mass relative to the perfluoroelastomer having iodine or bromine atoms. The content of polymer (I) 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, relative to the perfluoroelastomer having iodine or bromine atoms, as this further reduces the compression set of the resulting crosslinked product. 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 perfluoroelastomer having iodine or bromine atoms.

[0461] If the crosslinkable composition of this disclosure contains a perfluoroelastomer having an iodine atom or a bromine atom, the crosslinkable composition preferably contains an organic peroxide as a crosslinking agent. The organic peroxides described above can be suitably used.

[0462] If the crosslinkable composition of this disclosure contains a perfluoroelastomer having an iodine atom or a bromine atom, it is preferable to contain a crosslinking aid, and more preferably to contain an organic peroxide and a crosslinking aid. The above-mentioned crosslinking aids can be suitably used.

[0463] Next, we will describe perfluoroelastomers containing iodine or bromine atoms.

[0464] Perfluoroelastomers having iodine atoms or bromine atoms preferably have iodine atoms or bromine atoms at the main chain ends and / or side chains. Perfluoroelastomers having iodine atoms or bromine atoms may also have both iodine atoms and bromine atoms.

[0465] As the perfluoroelastomer having an iodine atom or a bromine atom, at least one selected from the group consisting of a perfluoroelastomer containing monomer units having an iodine atom or a bromine atom, a perfluoroelastomer having an iodine atom or a bromine atom at the main chain terminus, and a perfluoroelastomer having an iodine atom or a bromine atom at the main chain terminus and also containing monomer units having an iodine atom or a bromine atom is preferred.

[0466] Examples of monomers having an iodine atom or a bromine atom include: Formula:CX 4 2=CX 5 R f 2 -X (In the formula, X 4 , X 5 Each of these is independently H, F, or an alkyl group having 1 to 5 carbon atoms, and R f 2 Examples of monomers represented by (where X is a linear or branched alkylene group or oxyalkylene group which may have one or more ether-bonded oxygen atoms, may have an aromatic ring, and may have some or all of its hydrogen atoms substituted with fluorine atoms, and X is an iodine atom or a bromine atom).

[0467] Examples of monomers having an iodine atom or a bromine atom include: Formula:CX 16 2=CX 16 -Rf 16 CHR 16 X (In the formula, X 16 These are, independently, a hydrogen atom, a fluorine atom, or CH3, Rf 16 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group or a perfluoro(poly)oxyalkylene group, R 16 Fluoromers represented by a hydrogen atom or CH3, where X is an iodine atom or bromine atom, Formula:CX 16 2=CX 16 -Rf 17 X (In the formula, X 16 These are, independently, a hydrogen atom, a fluorine atom, or CH3, Rf 17 (where X 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) Formula: CF2 = CFO(CF2CF(CF3)O) m (CF2) n -X Fluoromers represented by the formula (wherein m is an integer from 0 to 5, n is an integer from 1 to 3, and X is an iodine atom, a bromine atom, or -CH2I), Equation: CH2 = CFCF2O(CF(CF3)CF2O) m (CF(CF3)) n -X Examples include monomers represented by the formula (where m is an integer from 0 to 5, n is an integer from 1 to 3, and X is an iodine atom or a bromine atom), which can be used individually or in any combination.

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

[0469] As the monomer having an iodine atom or a bromine atom, at least one selected from the group consisting of CF2=CFOCF2CF(CF3)OCF2CF2CH2I, CF2=CFOCF2CF2CH2I, and CH2=CHCF2CF2I is preferred, with CF2=CFOCF2CF2CH2I being more preferred.

[0470] Perfluoroelastomers having iodine or bromine atoms at the main chain ends can be produced by using an iodine or bromine compound as a chain transfer agent when polymerizing monomers to produce perfluoroelastomers. A polymerization method using an iodine or bromine compound includes, for example, emulsion polymerization in an aqueous medium under pressurized conditions in the presence of an iodine or bromine compound, in a substantially oxygen-free environment (iodine transfer polymerization). A typical example of an iodine or bromine compound used is, for example, one with the general formula: R 21 I x Br y (In the formula, x and y are integers from 0 to 2, and satisfy 1 ≤ x + y ≤ 2, R 21 Examples of compounds represented by 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 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, CF2Br2, BrCF2CF2Br, CF3CFBrCF2Br, CFClBr2, and BrCF Examples include 2CFClBr, CFBrClCFClBr, BrCF2CF2CF2Br, BrCF2CFBrOCF3, 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 derivatives of benzene, diiodomonobromo substituted derivatives, and (2-iodoethyl) and (2-bromoethyl) substituted derivatives, and these compounds may be used individually or in combination with each other.

[0472] Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are preferred in terms of polymerization reactivity, crosslinking reactivity, and availability.

[0473] The iodine and bromine content of the perfluoroelastomer having iodine or bromine atoms 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 and bromine content is too low, the haze value will be high, and a crosslinked material exhibiting excellent transparency may not be obtained. The iodine and bromine content can be measured by elemental analysis.

[0474] As the perfluoroelastomer having an iodine atom or a bromine atom, it is preferable to select at least one from the group consisting of perfluoroelastomers having an iodine atom or a bromine atom containing a TFE unit, for example, a fluoromonomer copolymer represented by general formula (160), (130), or (140), and a fluoromonomer / monomer copolymer having an iodine atom or a bromine atom represented by general formula (160), (130), or (140).

[0475] When the perfluoroelastomer having iodine or bromine atoms is a TFE / perfluoro(methyl vinyl ether) (PMVE) copolymer, the composition (mol%) of the perfluoroelastomer having iodine 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 or bromine atoms is a TFE / PMVE / monomer copolymer having iodine or bromine atoms, the composition (mol%) of the perfluoroelastomer having iodine or bromine atoms is preferably 45-89.9 / 10-54.9 / 0.01-4, more preferably 55-77.9 / 20-49.9 / 0.01-3.5, even more preferably 55-69.8 / 30-44.8 / 0.03-3.0, and most preferably 55.3-69.5 / 30.3-44.5 / 0.05-2.5.

[0477] When the perfluoroelastomer having an iodine atom or a bromine atom is a fluoromonomer copolymer represented by the general formula (160), (130), or (140) with 4 to 12 carbon atoms, the composition (mol%) of the perfluoroelastomer having an iodine atom or a bromine atom 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 an iodine atom or a bromine atom is a TFE / fluoromonomer represented by general formula (160), (130), or (140) with 4 to 12 carbon atoms / monomer copolymer having an iodine atom or a bromine atom, the composition (mol%) of the perfluoroelastomer having an iodine atom or a bromine atom 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 of these compositional ranges, the rubber-elastic properties are lost, and the material tends to become closer in properties to that of a resin.

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

[0480] Perfluoroelastomers containing iodine or bromine atoms are preferably glass transition temperatures of -70°C or higher, more preferably -60°C or higher, and even more preferably -50°C or higher, due to their excellent compression set properties at high temperatures. Furthermore, due to their 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 above glass transition temperature can be determined by using a differential scanning calorimeter (Mettler-Toledo, DSC822e) to obtain a DSC curve by heating 10 mg of the sample at 10°C / min, and then finding the temperature at the midpoint of the intersection of the extension of the baseline before and after the second-order transition of the DSC curve and the tangent line at the inflection point of the DSC curve.

[0482] Perfluoroelastomers having iodine or bromine atoms are preferably heat-resistant, with 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. Furthermore, in terms of good processability, the viscosity is preferably 120 or less, more preferably 100 or less, and even more preferably 80 or less.

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

[0484] In one embodiment of the crosslinkable composition of the present disclosure, the fluororubber contains a perfluoroelastomer having cyano groups.

[0485] When the crosslinkable composition of this disclosure contains a perfluoroelastomer having a cyano group, it can be crosslinked at a high crosslinking rate. This is because the content of polymer (I) in the above-mentioned composition contained in the crosslinkable composition of this disclosure is greatly reduced.

[0486] The content of polymer (I) in the crosslinkable composition of this disclosure is preferably 0.0001 to 1.0% by mass relative to the perfluoroelastomer having cyano groups. Since the crosslinking rate of the crosslinkable composition is further increased, the content of polymer (I) 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, relative to the perfluoroelastomer having cyano groups. 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 perfluoroelastomer having cyano groups.

[0487] If the crosslinkable composition of this disclosure contains a perfluoroelastomer having a cyano group, the crosslinkable composition may include an inorganic nitride, an organotin compound, an ammonia-generating compound, a compound having multiple 3-amino-4-hydroxyphenyl groups or 3-amino-4-mercaptophenyl groups, and general formula (47): [ka] (In the formula, R 41 , R 42 and R 43 It is preferable to contain at least one compound selected from the group consisting of compounds represented as (as described above). Inorganic nitrides, organotin compounds, ammonia-generating compounds, and the crosslinking agents thereof that are described above can be suitably used.

[0488] Next, we will describe perfluoroelastomers containing cyano groups.

[0489] Perfluoroelastomers having cyano groups (-CN groups) can be crosslinked by the cyano groups forming triazine rings through cyclization and trimerization, thereby imparting excellent compression set properties and heat resistance to the crosslinked material.

[0490] Perfluoroelastomers having cyano groups are preferably those having cyano groups (-CN groups) at the main chain terminus and / or side chains.

[0491] Perfluoroelastomers having cyano groups preferably contain monomer units having cyano groups. Examples of monomers having cyano groups include: Formula:CX 4 2=CX 5 R f 2 -CN (In the formula, X 4 , X 5 Each of these is independently H, F, or an alkyl group having 1 to 5 carbon atoms, and R f 2 Examples of monomers include those represented by a linear or branched alkylene group or oxyalkylene group, which may have one or more ether-bonded oxygen atoms, may have an aromatic ring, or may have some or all of its hydrogen atoms substituted with fluorine atoms.

[0492] Examples of monomers having a cyano group include, Formula:CY 1 2 = CY 1 (CF2) n -CN (In the formula, Y 1 (Each of these is either a hydrogen atom or a fluorine atom, and n is an integer between 1 and 8.) Formula: CF2=CFCF2Rf 8 -CN (In the formula, Rf 8 ha-(OCF2) n -or-(OCF(CF3)) n - where n is an integer between 0 and 5) Formula: CF2 = CFCF2(OCF(CF3)CF2) m (OCH2CF2CF2) n OCH2CF2-CN (In the formula, m is an integer between 0 and 5, and n is an integer between 0 and 5.) Formula: CF2=CFCF2(OCH2CF2CF2) m (OCF(CF3)CF2) nOCF(CF3)-CN (In the formula, m is an integer between 0 and 5, and n is an integer between 0 and 5.) Formula: CF2 = CF(OCF2CF(CF3)) m O(CF2) n -CN (In the formula, m is an integer between 0 and 5, and n is an integer between 1 and 8.) Formula: CF2 = CF(OCF2CF(CF3)) m -CN (In the formula, m is an integer between 1 and 5) Formula: CF2 = CFOCF2(CF(CF3)OCF2) n CF(-CN)CF3 (In the formula, n is an integer between 1 and 4.) Formula: CF2 = CFO(CF2) n OCF(CF3)-CN (In the formula, n is an integer between 2 and 5.) Formula: CF2 = CFO(CF2) n -(C6H4)-CN (In the formula, n is an integer between 1 and 6.) Formula: CF2 = CF(OCF2CF(CF3)) n OCF2CF(CF3)-CN (In the formula, n is an integer between 1 and 2.) Equation: CH2 = CFCF2O(CF(CF3)CF2O) n CF(CF3)-CN (In the formula, n is an integer between 0 and 5.) Formula: CF2 = CFO(CF2CF(CF3)O) m (CF2) n -CN (In the formula, m is an integer between 0 and 5, and n is an integer between 1 and 3.) Formula: CH2=CFCF2OCF(CF3)OCF(CF3)-CN Formula: CH2=CFCF2OCH2CF2-CN Formula: CF2 = CFO(CF2CF(CF3)O) m CF2CF(CF3)-CN (In the formula, m is a non-negative integer.) Formula: CF2 = CFOCF(CF3)CF2O(CF2) n -CN (In the formula, n is an integer greater than or equal to 1.) Formula: CF2=CFOCF2OCF2CF(CF3)OCF2-CN Examples include monomers represented by [the formula shown], which can be used individually or in any combination.

[0493] Among monomers having a cyano group (-CN group), Formula: CF2 = CF(OCF2CF(CF3)) m O(CF2) n -CN A monomer represented by the formula (where m is an integer from 0 to 5 and n is an integer from 1 to 8) is preferred, and CF2=CFOCF2CF(CF3)OCF2CF2CN is more preferred.

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

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

[0496] When the perfluoroelastomer having a cyano group is a TFE / fluoromonomer represented by general formula (160), (130), or (140) with 4 to 12 carbon atoms / monomer copolymer 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 of these compositional ranges, the rubber-elastic properties are lost, and the material tends to become closer in properties to that of a resin.

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

[0498] Perfluoroelastomers having cyano groups may have polar end groups. End groups refer to all groups located on the main chain of the polymer or on any long or short end. Polar end groups include carboxylates (-COO - ) group or sulfonate (-OSO3 - These include ionic groups such as ) groups, and nonionic groups such as alcohols (-CH2OH), acyl fluorides (-COF), and amides (-CONH2). Polar end groups can be introduced into elastomers by using inorganic peroxides as polymerization initiators when producing perfluoroelastomers by polymerizing monomers. The presence or absence of polar end groups can be confirmed by Fourier transform infrared spectroscopy (FTIR).

[0499] Perfluoroelastomers containing cyano groups are preferably glass transition temperatures of -70°C or higher, more preferably -60°C or higher, and even more preferably -50°C or higher, due to their excellent compression set properties at high temperatures. Furthermore, due to their 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 above glass transition temperature can be determined by using a differential scanning calorimeter (Mettler-Toledo, DSC822e) to obtain a DSC curve by heating 10 mg of the sample at 10°C / min, and then finding the temperature at the midpoint of the intersection of the extension of the baseline before and after the second-order transition of the DSC curve and the tangent line at the inflection point of the DSC curve.

[0501] The perfluoroelastomer having cyano groups is preferably heat-resistant, with a Mooney viscosity ML(1+20) at 170°C of 30 or higher, more preferably 40 or higher, and even more preferably 50 or higher. Furthermore, in terms of good processability, it is preferably 150 or lower, more preferably 120 or lower, and even more preferably 110 or lower.

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

[0503] The crosslinkable composition may contain fillers.

[0504] Suitable fillers include organic fillers, and from the viewpoint of heat resistance and plasma resistance (low particle size and low weight loss rate during 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, due to their excellent heat resistance, chemical resistance, and minimal impact on crosslinking properties.

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

[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 used individually or in combination of two or more types.

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

[0510] In fields where high purity and non-contamination are not particularly required, common additives used in perfluoroelastomers, such as processing aids, plasticizers, and colorants, may be added as needed, and one or more commonly used crosslinking agents or crosslinking aids different from those mentioned above may also be added.

[0511] The crosslinkable composition may contain an organic basic compound. An example of an organic basic compound is one with the formula: CH3(CH2) 17 - NH2 ocdadecylamine; Formula:H2N-C(O)-(CH2) 11 -CH=CH-(CH2)7CH3 elkaamide; Formula: Oleamide of H2N-C(O)-(CH2)7-CH=CH-(CH2)7CH3; Formula: Hexamethylenediamine of the form H2N-(CH2)6-NH2 formula: [ka] Examples include 1,8-diazabicycloundec-7-ene (DBU).

[0512] The crosslinkable composition can be prepared by mixing the above components using conventional polymer processing machinery, such as an open roll mixer, Banbury mixer, or kneader. Alternatively, it can also be prepared using a closed-type mixer.

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

[0514] The above crosslinking can be carried out in the order of primary crosslinking followed by secondary crosslinking. Primary crosslinking is preferably carried out at 150-250°C for 5-120 minutes, and more preferably at 160-200°C for 5-60 minutes. Any known crosslinking method can be used, such as press crosslinking.

[0515] Secondary crosslinking is preferably carried out at 150-320°C for 2-48 hours, and more preferably at 180-310°C for 3-24 hours. Any known crosslinking method can be used, such as oven crosslinking.

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

[0517] The crosslinked material of this disclosure can be suitably used as a sealing material for semiconductor manufacturing equipment that requires particularly high heat resistance, especially for semiconductor manufacturing equipment that undergoes high-density plasma irradiation. Examples of the sealing material include O-rings, square rings, gaskets, packings, oil seals, bearing seals, lip seals, and the like.

[0518] In addition, it can be used in 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 and lining material.

[0519] Furthermore, 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. Examples include the following:

[0520] (1) Etching apparatus Dry etching equipment Plasma etching equipment Reactive ion etching apparatus Reactive ion beam etching apparatus Sputter etching apparatus Ion beam etching system Wet etching apparatus Ashing device (2) Cleaning equipment Dry etching cleaning equipment UV / O3 cleaning system Ion beam cleaning system Laser beam cleaning device Plasma cleaning device Gas etching cleaning equipment Extraction and washing device Soxhlet extraction and washing apparatus High-temperature, high-pressure extraction and washing apparatus Microwave extraction and washing device Supercritical fluid extraction and washing apparatus (3) Exposure apparatus Stepper Kota Developer (4) Polishing equipment CMP equipment (5) Film deposition equipment CVD equipment Sputtering device (6) Diffusion and ion implantation device Oxidation diffusion device Ion implantation device

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

[0522] Furthermore, the crosslinked material of this disclosure has excellent heat resistance, oil resistance, amine resistance, chemical resistance, and cold resistance, and can be used in general parts that come into contact with other materials and slide, seal or encase other materials or substances, or for vibration damping and sound damping purposes, and can be used as various components in various fields such as the automotive industry, aerospace industry, and semiconductor industry. Examples of fields in which it is used include semiconductor-related fields, automotive fields, aircraft fields, space and rocket fields, shipbuilding fields, chemical fields such as chemical plants, pharmaceutical fields such as pharmaceuticals, photographic fields such as developing machines, printing fields such as printing machines, painting fields such as painting equipment, analytical and physicochemical machinery fields such as analytical instruments and measuring instruments, food machinery fields including food plant equipment and household goods, beverage and food manufacturing equipment fields, pharmaceutical manufacturing equipment fields, medical parts fields, chemical transport equipment fields, nuclear power plant equipment fields, steel fields such as sheet metal processing equipment, general industrial fields, electrical fields, fuel cell fields, electronic components fields, optical instrument components fields, space equipment components fields, petrochemical plant equipment fields, energy resource exploration and extraction equipment components fields such as oil and gas fields, petroleum refining fields, and petroleum transport equipment components fields.

[0523] Examples of applications for the crosslinked material of this 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 where heat resistance, solvent resistance, chemical resistance, and non-stick properties are required. It can also be used as a tube, hose, roll, various rubber rolls, flexible joint, rubber sheet, coating, belt, damper, valve, valve seat, valve body, chemical-resistant coating material, laminating material, lining material, and more. The cross-sectional shapes of the rings, packings, and seals mentioned above may vary. Specifically, they may be square, O-shaped, ferrule, or other shapes such as D-shaped, L-shaped, T-shaped, V-shaped, X-shaped, or Y-shaped.

[0524] In the semiconductor-related fields mentioned above, for example, it can be used in semiconductor manufacturing equipment, liquid crystal panel manufacturing equipment, plasma panel manufacturing equipment, plasma display panel manufacturing equipment, plasma address liquid crystal panel manufacturing equipment, organic EL panel manufacturing equipment, field emission display panel manufacturing equipment, solar cell substrate manufacturing equipment, semiconductor transport equipment, etc. Such equipment includes, for example, CVD equipment, gas control equipment such as gas control equipment for semiconductors, 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 deposition equipment, dry etching cleaning equipment, UV / O3 cleaning equipment, ion beam cleaning equipment, laser beam cleaning equipment, plasma cleaning equipment, and gas etching cleaning equipment. Examples include extraction and cleaning equipment, Soxhlet extraction and cleaning equipment, high-temperature and high-pressure extraction and cleaning equipment, microwave extraction and cleaning equipment, supercritical extraction and cleaning equipment, cleaning equipment using hydrofluoric acid, hydrochloric acid, sulfuric acid, ozonated water, etc., steppers, coaters and developers, CMP equipment, excimer laser exposure machines, chemical piping, gas piping, equipment for plasma treatment such as NF3 plasma treatment, O2 plasma treatment, and fluorine plasma treatment, heat treatment and film deposition equipment, wafer transport equipment, wafer cleaning equipment, silicon wafer cleaning equipment, silicon wafer processing equipment, equipment used in the LP-CVD process, equipment used in the lamp annealing process, and equipment used in the reflow process.

[0525] Specific applications in the semiconductor-related field include, for example, various sealing materials such as O-rings and gaskets for gate valves, quartz windows, chambers, chamber lids, gates, bell jars, couplings, and pumps; various sealing materials such as O-rings for resist developers and strippers, as well as hoses and tubes; linings and coatings for resist developer tanks, stripper tanks, wafer cleaning tanks, and wet etching tanks; pump diaphragms; rolls for wafer transport; hoses and tubes for wafer cleaning solutions; sealing materials for cleanrooms and other clean equipment such as sealants; sealing materials for storage facilities that store semiconductor manufacturing equipment and devices such as wafers; and diaphragms for chemical transfer used in the semiconductor manufacturing process.

[0526] In the automotive sector mentioned above, it can be used in the engine itself, main motion system, valve train, 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. Note that the automotive sector also includes motorcycles. In engine bodies and their peripheral equipment as described above, the crosslinked material of this disclosure can be used in various sealing materials that require heat resistance, oil resistance, fuel oil resistance, antifreeze resistance for engine cooling, and steam resistance. Examples of such sealing materials include seals such as gaskets, shaft seals, and valve stem seals; non-contact or contact type packings such as self-sealing packings, piston rings, split ring type packings, mechanical seals, and oil seals; bellows, diaphragms, hoses, and tubes; as well as various sealing materials used in electric wires, cushioning materials, vibration damping materials, and belt automatic transmission devices.

[0527] Specific applications in the above fuel system 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 breathing 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 subassemblies, 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 valve seals; fuel hoses, Hoses such as fuel supply hoses, fuel return hoses, vapor (evaporator) hoses, vent (breather) hoses, filler hoses, filler neck hoses, hoses inside the fuel tank (in-tank hoses), carburetor control hoses, fuel inlet hoses, fuel breather hoses, etc.; gaskets used in fuel filters, fuel line connector systems, etc., and flange gaskets used in carburetors, etc.; line materials such as vapor recovery lines, fuel feed lines, vapor / ORVR lines, etc.; diaphragms used in canisters, ORVRs, fuel pumps, fuel tank pressure sensors, gasoline pumps, carburetor sensors, combined air control (CAC) systems, pulsation dampers, canister diaphragms, autococks, etc., and pressure regulator diaphragms for fuel injection systems; valves for fuel pumps, carburetor needle valves, rollover check valves, check valves, etc.; vents (breathers), tubes used inside fuel tanks; tank packings for fuel tanks, etc., packings for carburetor accelerator pump pistons; fuel sender vibration damping parts for fuel tanks;Examples include O-rings and diaphragms for controlling fuel pressure; accelerator pump cups; in-tank fuel pump mounts; injector cushion rings and seal rings for fuel injectors; needle valve core valves for carburetors; accelerator pump pistons for carburetors; valve seats for combined air control (CAC) systems; fuel tank bodies; and sealing components for solenoid valves.

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

[0529] Specific examples of the above-mentioned basic electrical components include insulators and sheaths for electric wires (harnesses), tubes for harness exterior components, and grommets for connectors. Specific applications in control system electrical components include insulation materials for various sensor wires. Specific applications of the above-mentioned electrical components include O-rings and gaskets for car air conditioners, cooler hoses, high-pressure air conditioner hoses, air conditioner hoses, gaskets for electronic throttle units, plug boots for direct ignition systems, and diaphragms for distributors. It can also be used for bonding electrical components.

[0530] Specific applications in the above-mentioned intake and exhaust systems include packings used in intake manifolds, exhaust manifolds, etc., throttle body packings for throttles; diaphragms used in EGR (exhaust gas recirculation), pressure control (BPT), wastegates, turbo wastegates, actuators, actuators for variable turbine geometry (VTG) turbos, exhaust purification valves, etc.; hoses such as EGR control hoses, emission control hoses, turbo oil hoses (supply), turbo oil hoses (return), turbo air hoses, 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] Furthermore, it can be used in exhaust gas control components such as seals used in steam recovery canisters, catalytic converters, exhaust gas sensors, and oxygen sensors, as well as seals for solenoid armatures in steam recovery and steam canisters; and intake system manifold gaskets. Furthermore, it can be used in diesel engine components such as O-ring seals for direct injection injectors, rotary pump seals, control diaphragms, fuel hoses, EGR, priming pumps, and boost compensator diaphragms. It can also be used in O-rings, seals, hoses, tubes, and diaphragms used in urea SCR systems, as well as in the urea water tank body and seals for the urea water tank in urea SCR systems.

[0532] Specific examples of applications in the above-mentioned transmission system include transmission-related bearing seals, oil seals, O-rings, packings, and torque converter hoses. Other examples include transmission oil seals, automatic transmission oil hoses, ATF hoses, O-rings, and gaskets. Transmissions include AT (Automatic Transmission), MT (Manual Transmission), CVT (Continuously Variable Transmission), and DCT (Dual-Clutch Transmission). Other examples include oil seals, gaskets, O-rings, and packings for manual or automatic transmissions, as well as oil seals, gaskets, O-rings, and packings for continuously variable transmissions (belt-type or toroidal-type), packings for ATF linear solenoids, oil hoses for manual transmissions, ATF hoses for automatic transmissions, and CVTF hoses for continuously variable transmissions (belt-type or toroidal-type). Specific applications in steering systems include power steering oil hoses and high-pressure power steering hoses.

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

[0534] As such, specific examples of its use 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 systems, seals and bearing seals for exhaust gas re-combustion systems, hoses for re-combustion systems, diaphragms for carburetor sensors, vibration damping rubber (engine mounts, exhaust systems, muffler hangers, suspension bushings, center bearings, strut bumper rubber, etc.), vibration damping rubber for suspension (strut mounts, bushings, etc.), vibration damping rubber for drivetrain (dampers, etc.), fuel hoses, EGR tubes and hoses, twin carb tubes, core valves for carburetor needle valves, carburetor flange gaskets, oil hoses, oil cooler hoses, ATF hoses, cylinder head gaskets, water pump seals, gearbox seals, needle valve tips, reeds for motorcycle reed valves, oil seals for automobile engines, seals for gasoline hose guns, seals for car air conditioners, rubber hoses for engine intercoolers, fuel line connector devices.Seals for systems, CAC valves, needle tips, engine wiring, filler hoses, car air conditioning O-rings, intake gaskets, fuel tank materials, distributor diaphragms, water hoses, clutch hoses, power steering hoses, automatic transmission hoses, master cylinder hoses, heater hoses, air conditioning hoses, ventilation hoses, oil filler caps, power steering rack seals, rack and pinion boots, CVJ boots, ball joint dust covers, strut dust covers, weatherstrips, glass runs, center unit gaskets, body side welts, bumper rubbers, 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 Examples include 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, OPS 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 system 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 coatings, caliper seals, boots, wheel bearing seals, and bladders used in tire vulcanization molding.

[0535] In the aircraft, space / rocket, and marine sectors mentioned above, it can be used particularly in fuel systems and lubrication systems. In the aircraft sector, for example, these can be used as various aircraft seal components, various aircraft components for aircraft engine oil applications, jet engine valve stem seals, gaskets and O-rings, rotating shaft seals, hydraulic equipment gaskets, firewall seals, fuel supply hoses, gaskets and O-rings, aircraft cables, oil seals and shaft seals, etc.

[0536] In the aforementioned space and rocket fields, for example, it can be used as lip seals, diaphragms, and O-rings for spacecraft, jet engines, and missiles, as well as O-rings for gas turbine engine oils and vibration damping pads for missile ground control. Furthermore, in the marine sector, it can be used, for example, as a stern seal for the propeller shaft of a screw, a valve stem seal for the intake and exhaust of a diesel engine, a valve seal for a butterfly valve, a valve seat and shaft seal for a butterfly valve, a shaft seal for a butterfly valve, a stern tube seal, fuel hoses, gaskets, O-rings for engines, marine cables, marine oil seals, and marine shaft seals.

[0537] In the chemical and pharmaceutical fields, such as chemical plants, this technology can be used in processes that require a high degree of chemical resistance, such as those involved in the manufacture of pharmaceuticals, pesticides, paints, resins, and other chemical products. Specific applications in the above-mentioned chemical and pharmaceutical 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 instruments and physicochemical instruments (e.g., column fittings for analytical instruments and instruments), shrink joints for flue gas desulfurization systems, 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 instruments and instruments, chemical pumps, pump housings, valves, tachometers, etc., as well as O-rings for mechanical seals and compressor sealing; packings used in high-temperature vacuum dryers, tube joints of gas chromatography and pH meters, etc., and glass cooling systems for sulfuric acid production equipment. Examples include: instrument packing; diaphragms used in diaphragm pumps, analytical instruments, and scientific and chemical instruments; gaskets used in analytical instruments and instruments; ferrules used in analytical instruments and instruments; valve seats; U-cups; linings used in chemical equipment, gasoline tanks, wind tunnels, etc., and corrosion-resistant linings for anodized tanks; coatings for masking jigs for plating; valve components for analytical instruments and scientific and chemical instruments; expansion joints for flue gas desulfurization plants; acid-resistant hoses for concentrated sulfuric acid, etc., chlorine gas transfer hoses, oil-resistant hoses, rainwater drain hoses for benzene and toluene storage tanks; chemical-resistant tubes and medical tubes used in analytical instruments and scientific and chemical instruments; trichloroethylene-resistant rolls and dyeing rolls for textile dyeing; drug stoppers; medical rubber stoppers; chemical solution bottles, chemical solution tanks, bags, and chemical containers; and protective equipment such as gloves and boots that are resistant to strong acids and solvents.

[0538] In the fields of photography, such as developing machines; printing, such as printing presses; and painting, such as painting equipment, these can be used as rolls, belts, seals, valve components, etc., for dry-type photocopiers. Specific applications in the fields of photography, printing, and painting include: the surface layer of the transfer rolls of photocopiers, the cleaning blades and belts of photocopiers; rolls and belts for office automation equipment such as photocopiers, printers, and facsimile machines (e.g., fixing rolls, crimping rolls, and pressure rolls); rolls, roll blades, and belts for PPC photocopiers; rolls for 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; painting rolls, scrapers, tubes, and valve parts for coating and painting equipment; developing rolls, gravure rolls, guide rolls, guide rolls for magnetic tape manufacturing coating lines, gravure rolls for magnetic tape manufacturing coating lines, and coating rolls.

[0539] In the food equipment sector, including the aforementioned food plant equipment and household goods, it can be used in food manufacturing processes, or for food transfer or storage applications. Specific applications in the food processing equipment field include seals for plate heat exchangers, solenoid valve seals for vending machines, packings for electric kettle bottles, sanitary pipe packings, packings for pressure cookers, seals for water heaters, gaskets for heat exchangers, diaphragms and packings for food processing equipment, and rubber materials for food processing machines (for example, heat exchanger gaskets, diaphragms, various seals such as O-rings, piping, hoses, sanitary packings, valve packings, and filling packings used as joints between the mouth of a bottle or other container and the filler during filling). Other applications include packings, 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 mentioned above, it can be used for check valves and pressure reducing valves around the reactor, as well as seals in uranium hexafluoride enrichment equipment.

[0541] Specific applications in the above-mentioned 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 lubrication machinery; sealing materials used in mandrels, etc.; seals used in windows of dry cleaning equipment, etc.; seals for cyclotrons and (vacuum) valve seals; seals for proton accelerators; seals for automatic packaging machines; diaphragms for pumps used in sulfur dioxide and chlorine gas analyzers (pollution measuring instruments) in the air; snake pump linings; rolls and belts for printing presses; conveyor belts; pressing rolls for pickling steel plates, etc.; cables for robots; solvent pressing rolls for aluminum rolling lines, etc.; O-rings for couplers; acid-resistant cushioning materials; dust seals and lip rubbers for sliding parts of cutting machines; gaskets for food waste incinerators; friction materials; surface modifiers and coatings for metals or rubber. Furthermore, it can be used as gaskets and sealants for equipment used in the papermaking process, as a sealant for cleanroom filter units, as a sealing agent for buildings, as a protective coating agent for concrete and cement, as a glass cloth impregnation material, as a processing aid for polyolefins, as an additive to improve the moldability of polyethylene, as a fuel container for small generators and lawnmowers, and as pre-coated metal obtained by priming metal plates. In addition, it can be impregnated into woven fabrics and baked to be used as sheets and belts.

[0542] Specific examples of its use in the steel industry include sheet metal processing rolls in sheet metal processing equipment.

[0543] Specific applications in the electrical field include insulating oil caps for Shinkansen bullet trains, venting seals for liquid-sealed transformers, seals for transformers, jackets for oil well cables, seals for ovens such as electric furnaces, window frame seals for microwave ovens, sealant used when bonding the wedge and neck of a CRT, sealant for halogen lamps, fixing agent for electrical components, sealant for end treatment of sheathed heaters, and sealant used for insulating and moisture-proofing the terminals of electrical equipment lead wires. It can also be used as a covering material for oil-resistant and heat-resistant wires, high-temperature resistant wires, chemical-resistant wires, high-insulation wires, high-voltage transmission lines, cables, wires used in geothermal power generation equipment, and wires used around automobile engines. It can also be used as an oil seal or shaft seal for vehicle cables. Furthermore, it can be used in electrical insulation materials (for example, insulating spacers for various electrical equipment, insulating tapes used for cable joints and ends, and materials used in heat-shrinkable tubing) and electrical and electronic equipment materials used in high-temperature atmospheres (for example, lead wire materials for motors, and wire materials around high-temperature furnaces). It can also be used in the sealing layer and protective film (backsheet) of solar cells.

[0544] In the fuel cell field mentioned above, it 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 a seal, packing, and separator for piping for hydrogen, oxygen, generated water, etc.

[0545] In the field of electronic components mentioned above, it can be used as a raw material for heat dissipation materials, raw materials for electromagnetic wave shielding materials, gaskets for computer hard disk drives (magnetic recording devices), etc. It can also be used as a buffer rubber (crush 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 electrode of alkaline storage batteries, a binder for EL elements (electroluminescent elements), a binder for electrode active materials in capacitors, a encapsulant, a sealing agent, a coating material for quartz in optical fibers, a coating material for optical fiber coatings, and other films and sheets, as well as for potting, coating and adhesive sealing of electronic components and circuit boards, a fixing agent for electronic components, a modifier for encapsulants such as epoxy, a coating agent for printed circuit boards, a modifier for printed wiring board prepreg resins such as epoxy, a shatterproof material for light bulbs, etc., a gasket for computers, a large computer cooling hose, a gasket and O-ring packing for secondary batteries, especially lithium secondary batteries, a sealing layer that covers one or both sides of the outer surface of organic EL structures, a connector, a damper, etc.

[0546] In the field of chemical transport equipment mentioned above, it can be used in safety valves and loading valves for trucks, trailers, tank trucks, ships, etc.

[0547] In the field of equipment components for the exploration and extraction of energy resources such as oil and gas, these materials are used as various sealing materials used during the extraction of oil and natural gas, and as boots for electrical connectors used in oil wells. Specific applications in the field of energy resource exploration and mining equipment components include drill bit seals, pressure regulating diaphragms, seals for horizontal drilling motors (stators), stator bearing (shaft) seals, seals used in blowout prevention devices (BOPs), seals used in rotary blowout prevention devices (pipe wipers), seals and gas-liquid connectors used in MWDs (Real-time Drilling Information Detection Systems), logging tool seals used in logging equipment (e.g., O-rings, seals, packings, gas-liquid connectors, boots, etc.), expansion packers and completion packers and packer seals used therein, seals and packings used in cementing equipment, and perforators. Examples include seals used in drilling equipment, seals, packings and motor linings used in mud pumps, underground audible detector covers, U-cups, composition seating cups, rotary seals, laminated elastomeric bearings, flow control seals, sand volume control seals, safety valve seals, seals for hydraulic fracturing equipment, seals and packings for linear packers and linear hangers, seals and packings for well heads, seals and packings for chokes and valves, sealing materials for LWD (Logging During Drilling), diaphragms used in oil exploration and drilling applications (e.g., diaphragms for supplying lubricating oil to oil drilling pits), gate valves, electronic boots, and sealing elements for drilling guns.

[0548] In addition, it can be used for joint sealing in kitchens, bathrooms, and washrooms; tents for outdoor tents; seals for stamping materials; rubber hoses for gas heat pumps and CFC-resistant rubber hoses; agricultural films, linings, and weather-resistant covers; and tanks made of laminated steel plates used in construction, home appliances, and other fields.

[0549] Furthermore, it can also be used in articles that are combined with metals such as aluminum. Examples of such uses include door seals, gate valves, pendulum valves, solenoid tips, as well as metal-rubber parts combined with metal, such as piston seals, diaphragms, and metal gaskets. It can also be used for rubber parts, brake shoes, brake pads, and other components in bicycles.

[0550] Furthermore, a belt can be cited as one form of the crosslinked structure in this disclosure. Examples of the above-mentioned belts include: flat belts used in various high-temperature areas such as around engines of agricultural machinery, machine tools, and industrial machinery, as power transmission belts (including flat belts, V-belts, V-ribbed belts, toothed belts, etc.) and conveying belts (conveyor belts); conveyor belts for transporting bulk and granular materials such as coal, crushed stone, soil, ore, and wood chips in high-temperature environments; conveyor belts used in steel mills such as blast furnaces; conveyor belts used in applications exposed to high-temperature environments in precision equipment assembly plants, food processing plants, etc.; V-belts and V-ribbed belts for agricultural machinery, general equipment (e.g., office automation equipment, printing machines, commercial dryers, etc.), and automobiles; power transmission belts for conveying robots; toothed belts for food processing machinery and machine tool power transmission belts; and toothed belts used in automobiles, office automation equipment, medical equipment, printing machines, etc. In particular, timing belts are a typical example of toothed belts used in automobiles.

[0551] The above belt may have a single-layer structure or a multi-layer structure. In the case of a multilayer structure, the belt may consist of a layer obtained by crosslinking the crosslinkable composition of this disclosure and a layer made of other materials. In a multilayer belt, other layers may include layers made of other rubbers, layers made of thermoplastic resins, various fiber reinforcement layers, canvas, and metal foil layers.

[0552] The crosslinked material of this disclosure can also be used in industrial vibration damping pads, vibration damping mats, railway slab mats, pads, and automotive vibration damping rubber. Examples of automotive vibration damping rubber include those for engine mounts, motor mounts, member mounts, strut mounts, bushings, dampers, muffler hangers, and center bearings.

[0553] Other applications include joint components such as flexible joints and expansion joints, boots, and grommets. In the marine sector, for example, marine pumps are another example. Joint members are fittings used in piping and piping systems, and are used for purposes such as preventing vibrations and noise generated from piping systems, absorbing expansion and displacement due to temperature and pressure changes, absorbing dimensional changes, and mitigating and preventing the effects of earthquakes and ground subsidence. Flexible joints and expansion joints can be preferably used as complex-shaped molded products for applications such as shipbuilding piping, mechanical piping such as pumps and compressors, chemical plant piping, electrical piping, civil engineering and water supply piping, and automobiles. Boots can be preferably used as complex-shaped molded bodies for various industrial applications, such as automotive boots including constant velocity joint boots, dust covers, rack and pinion steering boots, pin boots, and piston boots; boots for agricultural machinery; boots for industrial vehicles; boots for construction machinery; boots for hydraulic machinery; boots for pneumatic machinery; boots for centralized lubrication systems; boots for liquid transfer systems; boots for fire fighting; and boots for various liquefied gas transfer systems.

[0554] The crosslinked material of this disclosure can also be used for diaphragms for filter presses, blowers, water supply diaphragms, liquid storage tanks, pressure switches, accumulators, air springs such as suspensions, and more.

[0555] By adding the crosslinked material of this disclosure to rubber or resin, an anti-slip agent can be obtained that provides molded products or coating films that are less slippery in wet environments such as rain, snow, ice, or sweat.

[0556] Furthermore, the crosslinked material of this disclosure can also be used as a cushioning material for hot press molding when manufacturing decorative plywood, printed circuit boards, electrical insulating boards, rigid polyvinyl chloride laminates, etc., using melamine resin, phenolic resin, epoxy resin, etc.

[0557] The crosslinking material of this disclosure can also contribute to the impermeability of various supports, such as weapon-related sealing gaskets and protective clothing against contact with invasive chemical agents.

[0558] Furthermore, it can 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 and seal lubricating oils (engine oil, transmission oil, gear oil, etc.), fuel oils, and greases (especially urea-based greases) that contain amine-based additives (especially amine-based additives used as antioxidants and detergent dispersants) used in transportation equipment such as automobiles and ships. It can also be used in tubes, hoses, various rubber rolls, coatings, belts, valve bodies, etc. It can also be used as a laminating material and lining material.

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

[0560] In addition, the crosslinked material of this disclosure may be used after forming a vulcanized coating. Specifically, applications include non-stick oil-resistant rolls for photocopiers, weatherstrips for preventing weather-induced de-icing, rubber stoppers for intravenous fluids, rubber stoppers for vials, mold release agents, non-stick light conveyor belts, anti-stick coatings for gaskets on automobile engine mounts, coatings for synthetic fibers, and bolt members or joints with a thin packing coating layer.

[0561] Furthermore, the automotive-related parts applications of the bridged structures described in this disclosure also include applications for motorcycle parts with similar structures. Furthermore, examples of fuels used in the automotive industry include diesel fuel, gasoline, and diesel engine fuel (including biodiesel fuel).

[0562] Furthermore, the crosslinkable composition of this disclosure can be used not only as a crosslinked product but also as various components in various industrial fields. Therefore, the applications of the crosslinkable composition of this disclosure will now be described. The crosslinkable composition of this disclosure can be used as a surface modifier for metals, rubber, plastics, glass, etc.; as a sealing material and coating material that requires heat resistance, chemical resistance, oil resistance, and non-stick properties, such as metal gaskets and oil seals; as a non-stick coating material or bleed barrier for rolls and belts for office automation equipment; and for impregnation and baking coating of woven sheets and belts. The crosslinkable composition of this disclosure can be used as a sealant, lining, or sealant for complex shapes by conventional means when it is made highly viscous and highly concentrated, can be used to form thin films of several microns in thickness when it is made highly viscous, and can be used to coat pre-coated metals, O-rings, diaphragms, and reed valves when it is made highly viscous. Furthermore, it can be used for coating woven fabrics, paper sheets, conveying rolls or belts, printing belts, chemical-resistant tubes, chemical stoppers, fuel hoses, and more.

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

[0564] The crosslinkable compositions of this disclosure can also be dissolved in solvents and used as paints and adhesives. They can also be used as paints in the form of emulsified dispersions (latex). The above composition is used as a sealing material or lining for various devices and piping, and 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 fibers. The above composition can be applied to a substrate or the like by a dispenser coating or screen printing coating.

[0565] The crosslinkable compositions of this 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 this disclosure may be used in the form of latex to manufacture coating fabrics, protective gloves, impregnated fibers, O-ring coatings, coatings for fuel system quick-connect O-rings, coatings for fuel system seals, coatings for fuel tank rollover valve diaphragms, coatings for fuel tank pressure sensor diaphragms, coatings for oil filters and fuel filter seals, coatings for fuel tank sender seals and sender head fitting seals, coatings for copier fixing mechanism rolls, and polymer coating compositions. They are useful for coating silicone rubber, nitrile rubber, and other elastomers. They are also useful for coating parts manufactured from such elastomers, for the purpose of improving both the permeability and chemical resistance of the base elastomer, as well as its thermal stability. Other applications include coatings for heat exchangers, expansion joints, butts, tanks, fans, flue ducts and other conduits, as well as for housing structures, such as concrete housing structures. The compositions may be applied to exposed cross-sections of multilayer component structures, for example, in the manufacturing of hose structures and diaphragms. Sealing members in connections and joints often consist of rigid materials, and the crosslinkable compositions of this disclosure provide improved frictional interfaces, enhanced dimensional interference fits with reduced trace leakage along the sealing surface. The latex enhances seal durability in various automotive system applications. These can also be used in the manufacture of power steering systems, fuel systems, air conditioning systems, and any joints where hoses and tubes connect to other parts. A further utility of the above compositions lies in the repair of manufacturing defects (and damage due to use) in multilayer rubber structures such as three-ply fuel hoses. The above compositions are also useful in coating thin steel sheets that can be formed or embossed before or after paint application. For example, multiple layers of coated steel can be assembled to form a gasket between two rigid metal members. The sealing effect is obtained by applying the crosslinkable compositions 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 strains in assembled parts, while providing good fuel savings and low emissions due to low crack, deflection, and hole strain.

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

[0567] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims.

[0568] <1> According to the first aspect of this disclosure, A composition is provided which contains a polymer (I) containing polymerization units (I) based on monomer (I) represented by general formula (I), and a fluororubber, wherein the content of polymer (I) is 0.0001 to 1.0% by 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 These are, independently, F, Cl, H, or CF3; X 2 is H, F, alkyl group or fluorine-containing alkyl group; A 0 is an anionic group; R is a linking group; Z 1 and Z 2 Each of these is independently H, F, an alkyl group, or a fluorinated alkyl group; m is an integer of 1 or more. <2> According to the second aspect of this disclosure, A composition is provided in which polymer (I) is a polymer (2) comprising polymerization units (2) based on monomer (2) represented by general formula (2). CX2 = CY(-O-Rf-A) (2) (wherein X is the same or different -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, -SO3M, -OSO3M or -C(CF3)2OM (M is H, a metal atom, NR) 74. Imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, 7 ( is H or an organic group.) <3> According to the third aspect of this disclosure, A composition is provided in which the fluororubber is a perfluoroelastomer, according to a first or second view. <4> According to the fourth aspect of this disclosure, A composition is provided that is substantially free of fluorine-containing surfactants according to any of the first to third viewpoints. <5> According to the fifth aspect of this disclosure, A polymerization dispersion containing polymer (I), the fluororubber, and an aqueous medium is prepared. A composition according to any of the first to fourth views is provided, obtained by contacting the fluororubber in the polymerization dispersion with an alcohol having 3 to 6 carbon atoms per OH group, thereby causing the fluororubber to coagulate. <6> According to the sixth aspect of this disclosure, A composition according to a fifth aspect is provided, wherein the number of carbon atoms per OH group of the alcohol is 3 to 5. <7> According to the seventh aspect of this disclosure, A composition according to a fifth or sixth aspect is provided, wherein the MolLogP of the alcohol is in the range of 0.3 to 1.6. <8> According to the eighth aspect of this disclosure, A polymerization dispersion containing polymer (I), the fluororubber, and an aqueous medium is prepared. A composition according to any of the first to fourth views is provided, obtained by freezing the polymerization dispersion to cause the fluororubber to coagulate. <9> According to the ninth aspect of this disclosure, A polymerization dispersion containing polymer (I), the fluororubber, and an aqueous medium is prepared. A composition according to any of the first to fourth views is provided, 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 cause the fluororubber to coagulate. 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> According to the tenth aspect of this disclosure, A composition according to any of the first to ninth aspects is provided, as well as a crosslinkable composition containing at least one selected from the group consisting of inorganic nitrides, organotin compounds, ammonia-generating compounds, and crosslinking agents. <11> According to the eleventh aspect of this disclosure, A crosslinkable composition according to a tenth aspect is provided, which contains a perfluoroelastomer having iodine atoms or bromine atoms as a fluororubber. <12> According to the 12th aspect of this disclosure, A crosslinkable composition according to an eleventh aspect is provided, which contains an organic peroxide as a crosslinking agent and further contains a crosslinking aid. <13> According to the 13th aspect of this disclosure, A crosslinkable composition is provided in which the perfluoroelastomer is at least one selected from the group consisting of a perfluorovinyl ether copolymer represented by general formula (140), a fluoromonomer represented by general formula (140) and a monomer copolymer having an iodine or bromine atom, a fluoromonomer copolymer represented by general formula (160), and a fluoromonomer represented by general formula (160) and a monomer copolymer having an iodine or bromine atom. General formula (140): CF2=CFO(CF2CF(Y 141 )O) m (CF2) n F (In the formula, Y 141(where m represents a fluorine atom or a trifluoromethyl group; where n is an integer from 1 to 4; where n is an integer from 1 to 4.) General formula (160): CF2=CF-ORf 161 (In the formula, Rf 161 (This represents a perfluoroalkyl group with 1 to 10 carbon atoms.) <14> According to the fourteenth aspect of this disclosure, The fluororubber contains a perfluoroelastomer having cyano groups. A crosslinkable composition according to a tenth aspect is provided. <15> According to the 15th aspect of this disclosure, Inorganic nitrides, organotin compounds, ammonia-generating compounds, compounds having multiple 3-amino-4-hydroxyphenyl groups or 3-amino-4-mercaptophenyl groups, and general formula (47): [ka] (In the formula, R 41 , R 42 and R 43 A crosslinkable composition according to a 14th aspect is provided, which contains at least one selected from the group consisting of compounds represented as above. <16> According to the sixteenth aspect of this disclosure, A crosslinkable composition according to a 14th or 15th aspect is provided, wherein the perfluoroelastomer is at least one selected from the group consisting of a tetrafluoroethylene / fluoromonomer / monomer copolymer having a cyano group represented by general formula (140) and a tetrafluoroethylene / fluoromonomer / monomer copolymer having a cyano group represented by general formula (160). General formula (140): CF2=CFO(CF2CF(Y 141 )O) m (CF2) n F (In the formula, Y 141 (where m represents a fluorine atom or a trifluoromethyl group; where n is an integer from 1 to 4; where n is an integer from 1 to 4.) General formula (160): CF2=CF-ORf161 (In the formula, Rf 161 (This represents a perfluoroalkyl group with 1 to 10 carbon atoms.) <17> According to the seventeenth aspect of this disclosure, A crosslinked product is provided, obtained by crosslinking a crosslinkable composition according to any of the 10th to 16th aspects. [Examples]

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

[0570] Each value in the examples was measured by the following method.

[0571] (Content of polymer (I) in dry fluororubber) A predetermined amount of polymer (I) was added to fluororubber without polymer (I) and thoroughly dispersed. The resulting fluororubber was formed into a film and measured using a Fourier transform infrared spectrometer (PerkinElmer). Absorption wavelength -CF(2213~2685cm) -1 ) and -COO (1600~1827cm -1 The ratio of absorbance areas was measured, and a calibration curve was created from the amount of added polymer (I). The fluororubber obtained in the examples and comparative examples was measured in the same manner, and the polymer (I) content was calculated from the calibration curve.

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

[0573] (Iodine atom content) It was measured by elemental analysis.

[0574] (Moony viscosity) The viscosity was measured using an ALPHA TECHNOLOGIES MV2000E Mooney viscometer at 170°C or 100°C, in accordance with JIS K6300.

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

[0576] Examples 1-7, 10-11 These embodiments show examples of coagulating fluororubber by coagulation method (1) or coagulation method (3).

[0577] 18 g of a polymerization dispersion of TFE / PMVE copolymer (polymer composition ratio TFE / PMVE = 60 / 40 mol%) containing 0.062 g of polymer (A) (a homopolymer of monomer A represented by the formula: CF2=CFOCF2CF2COOH) neutralized with aqueous ammonia (TFE / PMVE copolymer content 1.8 g) was dropped into 10 g of an alcohol or organic solvent with 3-6 carbon atoms per OH group, and the fluororubber was allowed to coagulate. After washing with water, it was dried at 75°C for 20 hours. The resulting dried fluororubber was formed into a film, and the polymer (A) content was measured using a Fourier transform infrared spectrometer.

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

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

[0580] Example 12 This embodiment shows an example of coagulating fluororubber by coagulation method (1).

[0581] 18 g of a polymerization dispersion of a TFE / PMVE copolymer (polymer composition ratio TFE / PMVE = 61 / 39 mol%) containing 0.048 g of polymer (B) (a homopolymer of monomer B represented by the formula: CF2=CFOCF2CF2SO3NH4) (TFE / PMVE copolymer content 1.8 g) was added dropwise to 10 g of 2-butanol to allow the fluororubber to coagulate. After washing with water, it was dried at 140°C for 12 hours. The polymer (B) content of the obtained dried fluororubber was measured by NMR.

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

[0583] The results are shown in Table 1. [Table 1]

[0584] Preparation Example 1 Polymerization was carried out in the same manner as in Example 11 described in International Publication No. 2022-107890, except that the amount of deionized water initially added was changed to 1561.5 g, and the polymer B aqueous solution B-2 was changed to polymer F aqueous solution F-2 (solid content concentration: 2.65% by mass) at 992.5 g, yielding 4027 g of an aqueous dispersion with a solid content concentration of 31.5% by mass. The polymerization time was 69.4 hours.

[0585] The obtained dispersion was post-treated using the method of Comparative Example 2 of this application to obtain 170 g of perfluoroelastomer. The obtained perfluoroelastomer was analyzed, and the following results were obtained. Perfluoroelastomer composition: TFE / PMVE = 66.3 / 33.7 mol% Iodine content: 0.44% by mass Mooney viscosity: ML1 + 10 (100℃) = 63.8 Glass transition temperature: -1.3℃

[0586] Example 13 850 g of an emulsified dispersion was prepared by performing the same procedure as in Example 11 described in International Publication No. 2022-107890, and the solid content of the dispersion was adjusted with water to the concentration shown in Table 2. This dispersion was added dropwise to 359 g of 2-BuOH adjusted to 71% with water, and coagulation was allowed to occur. The fluororubber was filtered off and washed with water as described in Table 2. That is, the fluororubber was washed four times using 1360 g of water. After that, the filtered fluororubber was vacuum dried at 140°C for 12 hours.

[0587] Example 14 Except for using the emulsified dispersion obtained in Preparation Example 1, the procedure was the same as in Example 13 for coagulation and drying.

[0588] Example 15 1700 g of an emulsified dispersion was prepared by performing the same procedure as in Example 4 described in International Publication No. 2022-107890, and the solid content of the dispersion 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, and coagulation was allowed. The fluororubber was filtered off and washed with water as described 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 followed, except that the dispersion obtained in Example 13 described in International Publication No. 2022-107890 was used.

[0590] Comparative Example 2 566 g of the emulsified dispersion obtained by performing the same procedure as in Example 11 described in International Publication No. 2022-107890 was adjusted with water to the solid content concentration shown in Table 2, and this dispersion was added dropwise to 4000 g of 10% hydrochloric acid aqueous solution while stirring. The coagulated fluororubber was filtered off and washed with water as described 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 followed, except that the dispersion obtained in Preparation Example 1 was used.

[0592] Comparative Example 4 850 g of the emulsified dispersion obtained by performing the same procedure as in Example 4 described in International Publication No. 2022-107890 was adjusted with water to the solid content concentration shown in Table 3, and this dispersion was added dropwise to 4000 g of a 10% hydrochloric acid aqueous solution while stirring. The coagulated fluororubber was filtered off and washed with water as described in Table 3. The filtered fluororubber was then vacuum dried at 70°C for 24 hours.

[0593] Comparative Example 5 The same procedure as in Comparative Example 4 was performed, except that the emulsified dispersion obtained by performing the same procedure as in Example 13 described in International Publication No. 2022-107890 was used.

[0594] To 100 parts by mass of the fluororubber obtained in Examples 13, 14, and Comparative Examples 2 and 3, 2 parts by mass of triallyl isocyanurate (TAIC, manufactured by Nippon Chemical Corporation) 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) as a filler were mixed in an open roll to prepare a crosslinkable fluororubber composition.

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

[0596] [Table 2]

[0597] <Crosslinkability> For the fluororubber composition, the crosslinking curve at the same temperature as press crosslinking was determined using the RPA2000 manufactured by ALPHA TECHNOLOGIES, and the optimal crosslinking time (T90) was found. <Normal physical properties> Using a 2mm thick crosslinked material, M100 (100% modulus, MPa), TB (tensile breaking strength, MPa), and tensile breaking elongation (EB, %) were measured in accordance with JIS-K6251. <Hardness> The hardness (Shore A) was measured (peak value) of a 2mm thick crosslinked material in accordance with JIS-K6253. <Compression permanent set> The compression set of the O-rings was measured under the conditions described in Tables 2 and 3, in accordance with the methods described in ASTM D395 or JIS K6262.

[0598] A crosslinkable fluororubber composition was prepared by mixing 100 parts by mass of the fluororubber obtained in Examples 15, 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.) as a filler, and kneading the mixture in an open roll.

[0599] The obtained fluororubber composition was crosslinked by pressing at 180°C for 40 minutes, and then further oven crosslinked at 290°C for 18 hours to produce 2 mm thick crosslinked material and O-rings (P-24). The results of various physical properties of the fluororubber composition and crosslinked material are shown in Table 3.

[0600] [Table 3]

Claims

1. A composition comprising a polymer (2) containing polymerization units (2) based on a monomer (2) represented by general formula (2), and fluororubber, wherein the content of polymer (2) is 0.0001 to 1.0% by mass relative to the fluororubber, A composition in which the fluororubber is a perfluoroelastomer. CX ２ =CY(-O-Rf-A) (2) (In the formula, X is the same or different -H or F, Y is -H, -F, an alkyl group or a fluorine-containing alkyl group, 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 (This is H or an organic group.)

2. The composition is F(CF ２ ) ７ COOM、 F(CF ２ ) ５ COOM、 H(CF ２ ) ６ COOM、 H(CF ２ ) ７ COOM、 CF ３ O(CF ２ ) ３ OCHFCF ２ AOM、 CF ３ (CF ２ ) ５ CH ２ CH ２ SO ３ M、 C ３ F ７ OCF(CF ３ )CF ２ OCF(CF ３ )COOM、 CF ３ CF ２ CF ２ OCF(CF ３ )COOM、 CF ３ CF ２ OCF ２ CF ２ OCF ２ COOM、 C ２ F ５ OCF(CF ３ )CF ２ OCF(CF ３ )COOM、 CF ３ OCF(CF ３ )CF ２ OCF(CF ３ )COOM、 CF ２ ClCF ２ CF ２ OCF(CF ３ )CF ２ OCF ２ COOM、 CF ２ ClCF ２ CF ２ OCF ２ CF(CF ３ )OCF ２ COOM、 CF ２ ClCF(CF ３ )OCF(CF ３ )CF ２ OCF ２ COOM、 CF ２ ClCF(CF ３ ) OCF ２ CF (CF ３ ) OCF ２ COOM, and 【Chemistry 41】 (In each formula, M is H, metal atom, NR ７ ４ , imidazolium which may have substituents, pyridinium which may have substituents, or phosphonium which may have substituents, ７ The composition according to claim 1, wherein is H or an organic group.) substantially does not contain a fluorine-containing surfactant selected from ).

3. A method for producing the composition according to claim 1 or 2, A polymerization dispersion containing polymer (2), the fluororubber, and an aqueous medium is prepared. A method for producing a composition, comprising the step of contacting the fluororubber in the polymerization dispersion with an alcohol having 3 to 6 carbon atoms per OH group to cause the fluororubber to coagulate.

4. A method for producing the composition according to claim 3, wherein the number of carbon atoms per OH group of the alcohol is 3 to 5.

5. A method for producing the composition according to claim 3, wherein the MolLogP of the alcohol is in the range of 0.3 to 1.

6.

6. A method for producing the composition according to claim 1 or 2, A polymerization dispersion containing polymer (2), the fluororubber, and an aqueous medium is prepared. A method for producing a composition, comprising the step of freezing the polymerization dispersion to cause the fluororubber to coagulate.

7. A method for producing the composition according to claim 1 or 2, A polymerization dispersion containing polymer (2), the fluororubber, and an aqueous medium is prepared. A method for producing a composition, comprising the step of 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

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

9. The crosslinkable composition according to claim 8, which contains a perfluoroelastomer having an iodine atom or a bromine atom as the perfluoroelastomer.

10. The crosslinkable composition according to claim 9, which contains an organic peroxide as a crosslinking agent and further contains a crosslinking aid.

11. The crosslinkable composition according to claim 9, wherein the perfluoroelastomer is at least one selected from the group consisting of a perfluorovinyl ether copolymer represented by general formula (140), a fluoromonomer represented by general formula (140) and a monomer copolymer having an iodine or bromine atom, a fluoromonomer copolymer represented by general formula (160), and a fluoromonomer represented by general formula (160) and a monomer copolymer having an iodine or bromine atom. General Formula (140): CF ２ =CFO(CF ２ CF(Y １４１ )O) ｍ (CF ２ ) ｎ F (In the formula, Y １４１ (where m represents a fluorine atom or a trifluoromethyl group; where n is an integer from 1 to 4; where n is an integer from 1 to 4.) General form (160): CF ２ =CF-ORf １６１ (wherein, Rf １６１ (This represents a perfluoroalkyl group with 1 to 10 carbon atoms.)

12. The crosslinkable composition according to claim 8, comprising a perfluoroelastomer having a cyano group as the perfluoroelastomer.

13. Inorganic nitrides, organotin compounds, ammonia-generating compounds, compounds having multiple 3-amino-4-hydroxyphenyl groups or 3-amino-4-mercaptophenyl groups, and general formula (47): 【Chemistry 39】 (In the formula, R ４１ Ha-SO ２ -, -O-, -CO-, alkylene groups with 1 to 6 carbon atoms, perfluoroalkylene groups with 1 to 10 carbon atoms, or single bonds, 【Chemistry 40】 is a group represented by, R ４２ and R ４３ one of which is -NH ２ and the other of which is -NHR ４４ , -NH ２ , -OH or -SH, and R ４４ is a hydrogen atom, a fluorine atom or a monovalent organic group), the crosslinkable composition according to claim 12, comprising at least one selected from the group consisting of compounds represented by

14. The crosslinkable composition according to claim 12, wherein the perfluoroelastomer is at least one selected from the group consisting of a tetrafluoroethylene / fluoromonomer / monomer copolymer having a cyano group represented by general formula (140) and a tetrafluoroethylene / fluoromonomer / monomer copolymer having a cyano group represented by general formula (160). General formula (140): CF ２ =CFO(CF ２ CF(Y １４１ )O) ｍ (CF ２ ) ｎ F (In the formula, Y １４１ (where m represents a fluorine atom or a trifluoromethyl group; where n is an integer from 1 to 4; where n is an integer from 1 to 4.) General form (160): CF ２ =CF-ORf １６１ (wherein, Rf １６１ (This represents a perfluoroalkyl group with 1 to 10 carbon atoms.)

15. A crosslinked product obtained by crosslinking the crosslinkable composition described in claim 8.

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