Compositions and molded articles containing fluorine-containing polymers

Abstract

To provide a composition that allows for the crosslinking of fluorine-containing polymers in a short time, and that yields molded articles with low compression set. [Solution] A composition containing a fluorine-containing polymer and composite particles, wherein the composite particles are composite particles on which an ammonia-generating compound is supported, the support is at least one selected from the group consisting of silicon carbide, alumina, titania, silica, zirconia, ceria, silica-alumina, calcia, magnesia, and carbon black, and the ammonia-generating compound is a compound that generates ammonia upon heating, is insoluble in perfluorohexane, and has a specific gravity less than that of perfluorohexane at 20°C.

Description

[Technical Field]

[0001] This disclosure relates to compositions and molded articles containing fluorine-containing polymers. [Background technology]

[0002] Patent Document 1 describes a curable perfluoroelastomer composition containing (A) a perfluoroelastomer which is a copolymer of tetrafluoroethylene, perfluoro(alkyl vinyl ether), and a nitrogen-containing monomer, (B) a compound which generates ammonia at 40 to 330°C, and (C1) water. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2011-021187 [Overview of the project] [Problems that the invention aims to solve]

[0004] The object of this disclosure is to provide a composition that can crosslink fluorine-containing polymers in a short time and produce molded articles with low compression set. [Means for solving the problem]

[0005] The present disclosure provides a composition comprising a fluorine-containing polymer and composite particles, wherein the composite particles are composite particles on which an ammonia-generating compound is supported, the support is at least one selected from the group consisting of silicon carbide, alumina, titania, silica, zirconia, ceria, silica-alumina, calcia, magnesia, and carbon black, and the ammonia-generating compound is a compound that generates ammonia upon heating, is insoluble in perfluorohexane, and has a specific gravity less than that of perfluorohexane at 20°C. [Effects of the Invention]

[0006] According to this disclosure, it is possible to provide a composition that can crosslink fluorine-containing polymers in a short time and produce molded articles with low compression set. [Modes for carrying out the invention]

[0007] The following describes specific embodiments of this disclosure in detail, but this disclosure is not limited to the embodiments described below.

[0008] The compositions of this disclosure contain a fluorine-containing polymer and composite particles.

[0009] 1. Composite particles The composite particles contain an ammonia-generating compound and a carrier.

[0010] The support material is at least one selected from the group consisting of silicon carbide, alumina, titania, silica (silicon oxide), zirconia, ceria, silica-alumina, calcia, magnesia, and carbon black. All of the support materials contained in the composite particles are insoluble in perfluorohexane and have a specific gravity greater than that of perfluorohexane at 20°C. Therefore, when only the support material is added to perfluorohexane at 20°C, the entire amount of the added support material sinks into the liquid.

[0011] As a support material, at least one selected from the group consisting of silicon carbide, alumina, titania, silica, and carbon black is preferred, and at least one selected from the group consisting of silicon carbide and silica is more preferred, as it can generate ammonia more efficiently, and therefore the fluorine-containing polymer can be crosslinked in a shorter time, resulting in a molded product with a smaller compression set.

[0012] The BET specific surface area of the carrier is preferably 5 to 300 m 2 / g, more preferably 15 m 2 / g or more, still more preferably 25 m 2 / g or more, even more preferably 35 m 2 / g or more, particularly preferably 50 m 2 / g or more, more preferably 250 m 2 / g or less, still more preferably 200 m 2 / g or less, even more preferably 150 m 2 / g or less, particularly preferably 100 m 2 / g or less.

[0013] The BET specific surface area of the carrier can be calculated by the BET method using a specific surface area measuring device. The BET method is a method of measuring the amount of gas (nitrogen gas) physically adsorbed on the particle surface when the particles are in a low-temperature state and calculating the specific surface area. For the measurement of the BET specific surface area, Macsorb HM-1208 manufactured by Mountech Co., Ltd. was used.

[0014] The moisture content of the carrier is preferably 10 mass ppm or more, more preferably 50 mass ppm or more, still more preferably 100 mass ppm or more, even more preferably 150 mass ppm or more, and particularly preferably 200 mass ppm or more because ammonia can be generated more efficiently, and thus the fluorine-containing polymer can be crosslinked in a shorter time, and a molded product with a smaller compression set can be obtained. The upper limit of the moisture content of the carrier is not particularly limited, but may be 20000 mass ppm or less, 17000 mass ppm or less, or 15000 mass ppm or less.

[0015] The moisture content of the carrier can be measured by a Karl Fischer moisture meter.

[0016] A carrier bulk density of 0.01 g / cm³ is preferable because it allows for more efficient ammonia generation, thus enabling the crosslinking of fluorine-containing polymers in a shorter time and resulting in molded articles with even lower compression set. 3 The above is more preferable, or 0.03 g / cm³. 3 The above is preferable, and more preferably 0.04 g / cm³ 3 The above is preferable, preferably 1.50 g / cm³ 3 The following, and more preferably 1.20 g / cm³ 3 The following, and more preferably 1.00 g / cm³ 3 The following, and more preferably 0.80 g / cm³ 3 The following applies:

[0017] The bulk density of the carrier is measured by taking W (g) of carrier particles as a sample, allowing this sample to fall naturally into a graduated cylinder, and then gently shaking it to obtain the apparent volume V (cm³) of the sample. 3 By keeping the constant and measuring its mass and volume, it can be calculated based on the following formula. Bulk density (g / cm³) 3 ) = Mass of the sample [W (g)] / Volume of the sample [V (cm³)] 3 )]

[0018] The ammonia-generating compounds contained in the composite particles are insoluble in perfluorohexane and have a specific gravity lower than that of perfluorohexane at 20°C. Therefore, when only the ammonia-generating compounds are added to perfluorohexane at 20°C, the entire amount of the added ammonia-generating compounds floats on the surface of the liquid.

[0019] In composite particles, the ammonia-generating compound is supported on a carrier. In this disclosure, if particles are added to perfluorohexane adjusted to a temperature of 20°C, the perfluorohexane is stirred for 1 minute, and after sufficient standing, the particles do not separate in the perfluorohexane, then it can be said that the ammonia-generating compound is supported on the carrier.

[0020] If the ammonia-generating compound is not supported on a carrier, but merely in contact with the carrier, some of the particles introduced into perfluorohexane will float on the surface, while the remaining particles will sink into the liquid.

[0021] On the other hand, in the case of composite particles in which an ammonia-generating compound is supported on a carrier, the entire amount of composite particles added to perfluorohexane will either float on the surface of the liquid or sink. The buoyancy or sinking of the composite particles is determined by the ratio of the ammonia-generating compound to the carrier within the composite particles.

[0022] The ammonia-generating compounds contained in the composite particles are compounds that generate ammonia when heated. In composite particles, the ammonia-generating compounds are supported on a carrier. Therefore, heating the composite particles allows for more efficient generation of ammonia than heating only the ammonia-generating compounds.

[0023] In one embodiment, by heating the composite particles, a larger amount of ammonia can be generated than when heating only the ammonia-generating compound, even if the heating temperature and heating time are the same.

[0024] In one embodiment, the amount of ammonia generated when the composite particles are heated at 180°C for 30 minutes is 1.1 times or more the amount of ammonia generated when only the ammonia-generating compound is heated at 180°C for 30 minutes. The amount of ammonia generated when the composite particles are heated at 180°C for 30 minutes may be 1.3 times or more, 1.5 times or more, 1.7 times or more, 1.9 times or more, 2.1 times or more, or 2.3 times or more, and may be 5.0 times or less, 4.5 times or less, 4.0 or less, or 3.5 times or less, compared to the amount of ammonia generated when only the ammonia-generating compound is heated at 180°C for 30 minutes. In this way, by heating the composite particles, a larger amount of ammonia can be generated compared to heating only the ammonia-generating compound.

[0025] In one embodiment, by heating the composite particles at a lower temperature than when heating only the ammonia-generating compound, it is possible to generate the same or greater amount of ammonia compared to when heating only the ammonia-generating compound. In another embodiment, by heating the composite particles at a temperature 20°C or more lower than when heating only the ammonia-generating compound, it is possible to generate the same or greater amount of ammonia compared to when heating only the ammonia-generating compound.

[0026] In one embodiment, the ammonia generation temperature of the composite particles is 70 to 300°C. Preferably, the ammonia generation temperature of the composite particles is 80°C or higher, more preferably 90°C or higher, even more preferably 100°C or higher, and still more preferably 110°C or higher. Furthermore, even when the composite particles are heated to a low temperature range of 180°C or lower, 170°C or lower, 160°C or lower, or 150°C or lower, a sufficient amount of ammonia is generated from the composite particles.

[0027] As described above, by heating the composite particles, it is possible to generate a larger amount of ammonia than when heating only the ammonia-generating compound, or to generate the same or greater amount of ammonia at a lower temperature. In other words, the composite particles used in this disclosure can efficiently generate ammonia.

[0028] The average particle size of the composite particles is preferably 0.01 to 200 μm, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, more preferably 150 μm or less, and even more preferably 100 μm or less, because it allows for sufficient dispersion in the composition, thus enabling crosslinking of the fluorine-containing polymer in a shorter time and obtaining molded articles with even smaller compression set. The average particle size of the composite particles is the median diameter determined by a laser diffraction particle size distribution analyzer. When the average particle size of the composite particles is within the above range, it tends to be easier to achieve a high level of balance between ammonia generation efficiency and the handlingability of the composite particles.

[0029] The content of the ammonia-generating compound in the composite particles is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 50% by mass or less, relative to the total mass of the ammonia-generating compound and the carrier.

[0030] When the carrier is silicon carbide, the content of the ammonia-generating compound in the composite particles is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 50% by mass or less, relative to the total mass of the ammonia-generating compound and the carrier.

[0031] When the carrier is silica, the content of the ammonia-generating compound in the composite particles can generate ammonia more efficiently, and therefore the fluorine-containing polymer can be crosslinked in a shorter time, resulting in a molded product with a smaller compression set. Therefore, the content of the ammonia-generating compound is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 50% by mass or less, relative to the total mass of the ammonia-generating compound and the carrier.

[0032] When the carrier is carbon black, the content of the ammonia-generating compound in the composite particles can generate ammonia more efficiently, and therefore the fluorine-containing polymer can be crosslinked in a shorter time, resulting in a molded product with a smaller compression set. Therefore, the content of the ammonia-generating compound is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, preferably 90% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less, relative to the total mass of the ammonia-generating compound and the carrier.

[0033] The melting point of the ammonia-generating compound is preferably 100 to 350°C, more preferably 120°C or higher, and more preferably 340°C or lower. In particular, by using an ammonia-generating compound that is solid below 100°C, the ammonia-generating compound can remain stable in the composite particles even when the composite particles are stored for a long period of time, improving the handling of the composite particles. Furthermore, because the ammonia-generating compound remains stable in the composite particles, it also remains stable in the composition, and as a result, even when the composition is stored for a long period of time, crosslinking of the fluorine-containing polymer is less likely to progress, improving the handling of the composition.

[0034] As for the ammonia-generating compound, at least one selected from urea, acetylurea, biuret, inorganic ammonium salts, N-phenylbenzamidine, and guanidines is preferred, more preferably at least one selected from urea, inorganic ammonium salts, and guanidines, and even more preferably urea.

[0035] Examples of guanidines include phenylguanidine, diphenylguanidine, cyanoguanidine, guanidine hydrochloride, and guanidine carbonate. An example of an inorganic ammonium salt is ammonium chloride.

[0036] 2. Method for manufacturing composite particles Composite particles can be manufactured by a manufacturing method that involves supporting an ammonia-generating compound on a carrier, for example, using a thermal plasma method, an impregnation-supported method, or a mechanical particle composite method.

[0037] One method for producing composite particles using the thermal plasma method is to supply a carrier into a thermal plasma flame to put the carrier into a gas phase state, rapidly cool the carrier in the gas phase state by supplying a cooling gas toward the terminal end of the thermal plasma flame to generate primary carrier particles, and then supply an ammonia-generating compound to the primary carrier particles to support the ammonia-generating compound on the primary carrier particles.

[0038] The temperature of the thermal plasma flame must be higher than the boiling point of the carrier. For example, the temperature of the thermal plasma flame can be set to 6000°C. The atmospheric pressure of the thermal plasma flame is preferably below atmospheric pressure, for example, 0.5 to 100 kPa. The shape of the carrier supplied into the thermal plasma flame is preferably in powder form. The supply of the ammonia-generating compound to the primary fine particles can be carried out, for example, by spraying an aqueous solution of the ammonia-generating compound onto the primary fine particles. The aqueous solution of the ammonia-generating compound is preferably sprayed into an atmosphere in which the ammonia-generating compound does not thermally decompose. The droplets containing the sprayed ammonia-generating compound come into contact with the primary fine particles, the solvent then evaporates, and the ammonia-generating compound precipitates on the primary fine particles.

[0039] One method for producing composite particles using the impregnation-supporting method involves adding a support to a solution of an ammonia-generating compound and evaporating the solvent to support the ammonia-generating compound on the support. The solution of the ammonia-generating compound is preferably an aqueous solution or an alcoholic solution. The solvent is preferably water or alcohol.

[0040] The mechanical particle compounding method is a method of producing composite particles by applying mechanical forces such as compressive force, shear force, frictional force, and impact force while mixing an ammonia-generating compound with a carrier, thereby coating the surface of the carrier with the ammonia-generating compound. For example, one method is to mix the ammonia-generating compound and the carrier while crushing them using a mortar and pestle. In a method in which the ammonia-generating compound and carrier are placed in a bag and the bag is shaken, no mechanical force is applied to the ammonia-generating compound or the carrier, so the ammonia-generating compound cannot be supported on the carrier.

[0041] 3. Fluorine-containing polymers The compositions disclosed herein contain a fluorine-containing polymer. A fluorine-containing elastomer is preferred as the fluorine-containing polymer due to its excellent sealing properties, chemical resistance, and heat resistance.

[0042] In this disclosure, "fluorine-containing elastomer" refers to an amorphous fluorine-containing polymer. "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 fluorine-containing polymer is 4.5 J / g or less. Fluorine-containing elastomers exhibit elastomer 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.

[0043] The fluorine-containing elastomer may be a partially fluorinated elastomer or a perfluoroelastomer, but it is preferable to use a perfluoroelastomer because it has even better chemical resistance and heat resistance.

[0044] In this disclosure, a partially fluorinated elastomer is a fluorinated polymer containing fluoromonomer units, having a perfluoromonomer unit content of less than 90 mol% relative to the total monomer 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.

[0045] In this disclosure, a perfluoroelastomer is a fluorine-containing polymer having a perfluoromonomer unit content of 90 mol% or more, preferably 91 mol% or more, relative to the total monomer 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 fluorine-containing polymer is calculated from the types and content of each monomer constituting the fluorine-containing polymer.

[0046] 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.

[0047] Examples of the partially fluorinated elastomers mentioned above 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, and ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE)-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.

[0048] 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. 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.

[0049] In this disclosure, the content of each monomer constituting the fluorine-containing polymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0050] Other monomers copolymerizable with the above vinylidene fluoride include TFE, HFP, fluoroalkyl vinyl ether, chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, and general formula (1): CH2=CFRf 1 (In the formula, Rf 1 Fluoromers represented by a straight-chain or branched fluoroalkyl group having 1 to 12 carbon atoms, general formula (2): CH2=CH-(CF2) n -X2 (In the formula, X 2 Fluoromers represented by ) are H or F, and n is an integer from 3 to 10; monomers that provide crosslinking sites; 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, fluoroalkyl vinyl ether, and CTFE.

[0051] The above fluoroalkyl vinyl ethers include: General formula (3): CF2=CF-ORf 3 (In the formula, Rf 3 ) represents a perfluoroalkyl group having 1 to 8 carbon atoms. General formula (4): CF2=CFOCF2ORf 4 (In the formula, Rf 4 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 (5): CF2=CFO(CF2CF(Y 5 )O) m (CF2) n F (In the formula, Y 5 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 It is preferably at least one selected from the group consisting of the above, and more preferably a fluoromonomer represented by general formula (3).

[0052] 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 (1), VDF / fluoromonomer / TFE rubber represented by general formula (1), VDF / perfluoro(methyl vinyl ether) [PMVE] rubber, VDF / PMVE / TFE rubber, and VDF / PMVE / TFE / HFP rubber. Among the fluoromonomer rubber represented by VDF / general formula (1), VDF / CH2=CFCF3 rubber is preferred, and among the fluoromonomer / TFE rubber represented by VDF / general formula (1), VDF / TFE / CH2=CFCF3 rubber is preferred.

[0053] 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 15 to 50 mol% CH2=CFCF.

[0054] 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.

[0055] The above-mentioned fluorine-containing elastomer may be a perfluoroelastomer. The above-mentioned perfluoroelastomer is preferably at least one selected from the group consisting of a perfluoroelastomer containing TFE, for example, a TFE / fluoromonomer copolymer represented by general formula (3), (4), or (5), and a fluoromonomer / monomer copolymer that provides a crosslinking site represented by general formula (3), (4), or (5).

[0056] 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 60-75 / 25-40.

[0057] In the case of monomer copolymers that provide TFE / PMVE / crosslinking sites, the preferred values ​​are 45-90 / 10-54.9 / 0.01-4 (mol%), more preferably 50-78 / 20-49.9 / 0.1-3.5, and even more preferably 60-74.7 / 25-39.2 / 0.3-2.

[0058] In the case of a fluoromonomer copolymer represented by general formula (3), (4), or (5) 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.

[0059] In the case of TFE / fluoromonomers represented by general formulas (3), (4), or (5) with 4 to 12 carbon atoms / monomer copolymers that provide crosslinking sites, 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. 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.

[0060] The perfluoroelastomer is preferably at least one selected from the group consisting of TFE / fluoromonomer represented by general formula (5) / monomer copolymer that provides a crosslinking site, TFE / fluoromonomer copolymer represented by general formula (5), TFE / fluoromonomer copolymer represented by general formula (3), and TFE / fluoromonomer / monomer copolymer that provides a crosslinking site.

[0061] Examples of the above-mentioned perfluoroelastomers 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.

[0062] A monomer that provides crosslinking sites is a monomer (curation site monomer) that has crosslinkable groups that provide crosslinking sites to a fluoropolymer for crosslinking by a crosslinking agent.

[0063] As monomers that provide crosslinking sites, General formula (6):CX 6 2=CX 6 -Rf 6 CHR 6 X 7 (In the formula, X 6 These are the same or different hydrogen atoms, fluorine atoms, or CH3, Rf 6 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group or a perfluoro(poly)oxyalkylene group, R 6 is a hydrogen atom or CH3, X 7 Fluoromers represented by an iodine atom or a bromine atom, General formula (7):CX 6 2=CX 6 -Rf 7 X 7 (In the formula, X 6 These are the same or different hydrogen atoms, fluorine atoms, or CH3, Rf 7 X is a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group or a perfluoro(poly)oxyalkylene group, X 7 Fluoromers represented by an iodine atom or a bromine atom, General formula (8): CF2=CFO(CF2CF(CF3)O) m (CF2) n -X 8 (In the formula, m is an integer from 0 to 5, n is an integer from 1 to 3, X 8Fluoromers represented by a cyano group, carboxyl group, alkoxycarbonyl group, iodine atom, bromine atom, or -CH2I, General formula (9): CH2=CFCF2O(CF(CF3)CF2O) m (CF(CF3)) n -X 9 (In the formula, m is an integer from 0 to 5, n is an integer from 1 to 3, X 9 Fluoromers represented by a cyano group, carboxyl group, alkoxycarbonyl group, iodine atom, bromine atom, or CH2OH, and General formula (10):CR 10 2=CR 10 -Z-CR 10 =CR 10 2 (In the formula, R 10 Z is either the same or different hydrogen atom or a C1-C5 alkyl group. Z is a linear or branched alkylene group having an oxygen atom, having C1-C18, a cycloalkylene group having C3-C18, a C1-C10 alkylene group or oxyalkylene group that is at least partially fluorinated, or -(Q) p -CF2O-(CF2CF2O) m (CF2O) n -CF2-(Q) p - It is preferable that the monomer is at least one selected from the group consisting of monomers 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 has a molecular weight of 500 to 10000.

[0064] X 6 It is preferably a fluorine atom. Rf 6 and Rf 7 It is preferable that it is a perfluoroalkylene group having 1 to 5 carbon atoms. 6 It is preferably a hydrogen atom. 8It is preferable that this is a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2I. 9 It is preferable that the component is a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2OH.

[0065] Examples of monomers that provide the crosslinking site include CF2=CFOCF2CF(CF3)OCF2CF2CN, CF2=CFO(CF2)3CN, CF2=CFOCF2CF(CF3)OCF2CF2COOH, CF2=CFOCF2CF(CF3)OCF2CF2CH2I, CF2=CFOCF2CF2CH2I, CH2=CFCF2OCF(CF3)CF2OCF(CF3)CN, CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOH, and CH2=CF It is preferable that it be at least one selected from the group consisting of CF2OCF(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.

[0066] The above-mentioned fluorine-containing elastomer is preferably such that its glass transition temperature is -30°C or higher, more preferably -20°C or higher, and even more preferably -10°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 10°C or lower, more preferably 5°C or lower, and even more preferably 0°C or lower.

[0067] 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.

[0068] The above-mentioned fluorine-containing elastomer is preferably heat-resistant, and more 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 is preferably 150 or lower, more preferably 120 or lower, and even more preferably 110 or lower.

[0069] The above-mentioned fluorine-containing elastomer is preferably heat-resistant, and more 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 is preferably 180 or lower, more preferably 150 or lower, and even more preferably 110 or lower.

[0070] The above-mentioned fluorine-containing elastomer is preferably heat-resistant, and more 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. Furthermore, in terms of good processability, it is preferably 120 or less, more preferably 100 or less, and even more preferably 80 or less.

[0071] 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.

[0072] The partially fluorinated elastomers and perfluoroelastomers described above can be produced by conventional methods, but iodine compounds or bromine compounds can also be used as chain transfer agents because they result in a narrow molecular weight distribution of the resulting polymers, allow for easy control of molecular weight, and enable the introduction of iodine or bromine atoms at the terminals. A polymerization method using iodine compounds or bromine compounds 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 11 I x Br y (In the formula, x and y are integers from 0 to 2, and satisfy 1 ≤ x + y ≤ 2, R 11 Examples of compounds are those 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). By using an iodine compound or a bromine compound, an iodine atom or a bromine atom is introduced into the polymer and functions as a crosslinking point.

[0073] Examples of iodine and bromine compounds include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, 1-bromo-4-iodoperfluorobutane, and the like. These compounds may be used individually or in combination with each other.

[0074] Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are preferred in terms of polymerization reactivity, crosslinking reactivity, and availability.

[0075] The above-mentioned fluorine-containing polymer is preferably a fluorine-containing elastomer having cyano groups (-CN groups) at the ends of the main chain and / or at the side chains. Fluorine-containing elastomers having cyano groups (-CN groups) at the ends of the main chain and / or at the side chains can be crosslinked by the cyano groups forming triazine rings through cyclization trimerization, which can impart excellent compression set resistance and heat resistance to molded articles.

[0076] Examples of fluorine-containing elastomers having cyano groups (-CN groups) at the ends of the main chain and / or side chains include perfluoroelastomers and partially fluorinated elastomers.

[0077] Examples of perfluoroelastomers having cyano groups (-CN groups) at the main chain ends and / or side chains include the TFE / fluoromonomer represented by general formulas (3), (4), or (5) / monomer copolymers that provide crosslinking sites, in which the monomer providing the crosslinking sites is a monomer having cyano groups (-CN groups). In this case, the content of monomer units having cyano groups (-CN 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 (3), (4), and (5), from the viewpoint of good crosslinking properties and heat resistance. More preferred compositions are as described above.

[0078] Furthermore, examples of monomers having a cyano group (-CN group) include, Formula:CY 1 2 = CY 1 (CF2) n -CN (In the formula, Y 1 (These are either the same or different hydrogen atoms or fluorine atoms, and n is an integer from 1 to 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 (where m is an integer from 0 to 5 and n is an integer from 0 to 5) Formula: CF2=CFCF2(OCH2CF2CF2) m (OCF(CF3)CF2) n OCF(CF3)-CN (where m is an integer from 0 to 5 and n is an integer from 0 to 5) Formula: CF2=CF(OCF2CF(CF3)) m O(CF2) n -CN (where m is an integer from 0 to 5 and n is an integer from 1 to 8) Formula: CF2=CF(OCF2CF(CF3)) m -CN (where m is an integer from 1 to 5) Formula: CF2=CFOCF2(CF(CF3)OCF2) n CF(-CN)CF3 (where n is an integer from 1 to 4) Formula: CF2=CFO(CF2) n OCF(CF3)-CN (where n is an integer from 2 to 5) Formula: CF2=CFO(CF2) n -(C6H4)-CN (where n is an integer from 1 to 6) Formula: CF2=CF(OCF2CF(CF3)) n OCF2CF(CF3)-CN (where n is an integer from 1 to 2) Formula: CH2=CFCF2O(CF(CF3)CF2O) n CF(CF3)-CN (where n is an integer from 0 to 5), Formula: CF2=CFO(CF2CF(CF3)O) m (CF2) n -CN (where m is an integer from 0 to 5 and n is an integer from 1 to 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 Formula: CF2 = CFO(CF2) n CN (In the formula, n is an integer greater than or equal to 1) Examples include monomers represented by [the formula shown], which can be used individually or in any combination.

[0079] Among the above, Formula: CF2 = CF(OCF2CF(CF3)) m O(CF2) n -CN (In the formula, m is an integer from 0 to 5, and n is an integer from 1 to 8), or, Formula: CF2 = CFO(CF2) n CN A monomer represented by the formula (where n is an integer of 1 or more) is preferred, and CF2 = CFOCF2CF(CF3)OCF2CF2CN is more preferred.

[0080] Since these monomers have cyano groups, these cyano groups undergo a cyclization-trimerization reaction, leading to the formation of triazine bridges.

[0081] These perfluoroelastomers can be manufactured by conventional methods.

[0082] Specific examples of such perfluoroelastomers include fluororubbers described in International Publication No. 97 / 24381, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, and Japanese Patent Publication No. 5-13961, among others.

[0083] Examples of partially fluorinated elastomers having cyano groups (-CN groups) at the ends of the main chain and / or side chains include vinylidene fluoride (VdF)-based fluororubber, tetrafluoroethylene (TFE) / propylene-based fluororubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF)-based fluororubber, ethylene / hexafluoroethylene (HFP)-based fluororubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF)-based fluororubber, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE)-based fluororubber, fluorosilicone-based fluororubber, or fluorophosphazene-based fluororubber, which can be used individually or in any combination as long as it does not impair the effects of the present disclosure.

[0084] A vinylidene fluoride-based fluororubber refers to a fluorine-containing copolymer consisting of 45 to 85 mol% vinylidene fluoride and 55 to 15 mol% of at least one other monomer copolymerizable with vinylidene fluoride. Preferably, it refers to a fluorine-containing copolymer consisting of 50 to 80 mol% vinylidene fluoride and 50 to 20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.

[0085] Examples of at least one other monomer copolymerizable with vinylidene fluoride include fluoromonomers such as TFE, CTFE, trifluoroethylene, HFP, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, perfluoro(alkyl vinyl ether) (PAVE), and vinyl fluoride, as well as non-fluorinated monomers such as ethylene, propylene, and alkyl vinyl ether. These can be used individually or in any combination. Among these, TFE, HFP, and perfluoro(alkyl vinyl ether) are preferred.

[0086] Specific examples of rubber include VdF-HFP rubber, VdF-HFP-TFE rubber, VdF-CTFE rubber, and VdF-CTFE-TFE rubber.

[0087] Tetrafluoroethylene / propylene-based fluororubber refers to a fluorine-containing copolymer consisting of 45-70 mol% tetrafluoroethylene and 55-30 mol% propylene, further containing 0-5 mol% of monomers that provide crosslinking sites relative to the total amount of tetrafluoroethylene and propylene.

[0088] Examples of monomers that provide crosslinking sites include cyano group-containing monomers as described in Japanese Patent Publication No. 4-505345 and Japanese Patent Publication No. 5-500070, and monomers having the aforementioned cyano group (-CN group).

[0089] These partially fluorinated elastomers can be manufactured by conventional methods.

[0090] Alternatively, a thermoplastic fluororubber consisting of an elastomerable fluorine-containing polymer chain segment and a non-elastomerable fluorine-containing polymer chain segment may be used as the fluorine-containing elastomer.

[0091] 4. Composition The compositions of this disclosure contain a fluorine-containing polymer and composite particles. When the fluorine-containing polymer in the compositions of this disclosure has cyano groups, heating the compositions of this disclosure generates ammonia from the composite particles, which cyclizes and trimers the cyano groups of the fluorine-containing polymer to form a triazine ring, thereby crosslinking the fluorine-containing polymer.

[0092] Since the composition of this disclosure contains composite particles in which a fluorine-containing polymer and an ammonia-generating compound are supported on a carrier, compared to compositions containing a fluorine-containing polymer, an ammonia-generating compound, and a carrier (a carrier without the ammonia-generating compound), the fluorine-containing polymer can be crosslinked in a short time, and a molded article with low compression set can be obtained. This is presumed to be because the composite particles contained in the composition of this disclosure can efficiently generate ammonia.

[0093] The content of composite particles in the composition of this disclosure is preferably 0.1 to 100 parts by mass, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, even more preferably 1.0 part by mass or more, more preferably 10 parts by mass or less, even more preferably 7.0 parts by mass or less, and even more preferably 5.0 parts by mass or less, per 100 parts by mass of fluorine-containing polymer, in order to enable crosslinking of the fluorine-containing polymer in a shorter time, to obtain a molded article with an even smaller compression set, and from the viewpoint of cleanliness.

[0094] The optimal crosslinking time (T90) of the compositions of this disclosure at 180°C may be 5 minutes or less, 4 minutes or less, or 3 minutes or less, and may be 30 seconds or more.

[0095] Crosslinking agents are not essential components. However, the compositions of this disclosure may further contain crosslinking agents.

[0096] Examples of the crosslinking agents mentioned above include those used in peroxide crosslinking, polyol crosslinking, polyamine crosslinking, triazine crosslinking, oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking.

[0097] 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, for example, 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 (Permil D, Permil D-40, Permil D-40MB(T)), α,α-bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di( Examples include t-butylperoxy)hexane (perhexa 25B, perhexa 25B-40), 2,5-dimethyl-2,5-di(t-butylperoxy)-hexyn-3 (perhexyn 25B, perhexyn 25B-40), benzoyl peroxide, t-hexyl peroxypivalate (perhexyl PV, perhexyl PV-50E), t-butyl peroxypivalate (perbutyl PV, perbutyl PV-40E), polymer blends of t-butylperoxy-3-methylbenzoate and t-butylperoxybenzoate (perbutyl ZT), and t-butylperoxybenzoate (perbutyl Z). 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-, the decomposition temperature, etc.

[0098] 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.

[0099] 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.

[0100] 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 represented by the group (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. The compound represented by general formula (33) is preferably F2C=CF-O-(CF2)3-O-CF=CF2 or F2C=CF-O-(CF2)5-O-CF=CF2.

[0101] Crosslinking agents, or crosslinking aids used with peroxide crosslinking agents, include general formula (35): [ka]

[0102] (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.

[0103] Compounds having a structure represented by general formula (36) include general formula (36): [ka]

[0104] (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]

[0105] (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 ().

[0106] 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.

[0107] Examples of crosslinking agents used for polyol crosslinking include polyhydric alcohol compounds such as bisphenol A and bisphenol AF.

[0108] 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.

[0109] Examples of crosslinking agents used for oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking include, for example, general formula (41):

[0110] [ka]

[0111] (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,

[0112] [ka]

[0113] 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 R 42 is -NH2 and R 43 ga-NHR 44Preferred 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,

[0114] [ka]

[0115] 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):

[0116] [ka] (R 41 As mentioned above, R 45 Each of these is independently one of the following bases. [ka]

[0117] A bisamido-razone crosslinking agent represented by general formula (43):

[0118] [ka]

[0119] (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):

[0120] [ka]

[0121] 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).

[0122] 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 nitrile 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 given, which is selected from the group consisting of oligomers containing copolymer units of tetrafluoroethylene and hydrocarbon olefins.

[0123] 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):

[0124] [ka]

[0125] (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.

[0126] Among these, 2,2-bis[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane is preferred in terms of heat resistance, steam resistance, amine resistance, and good crosslinking properties.

[0127] The content of the above 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 the fluorine-containing polymer.

[0128] The compositions of this disclosure may contain fillers (except for the composite particles described above).

[0129] Examples of fillers include imide-based fillers having an imide structure such as polyimide, polyamideimide, and polyetherimide; organic fillers made of engineering plastics such as polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyoxybenzoate; metal oxide fillers such as aluminum oxide, silicon oxide, and yttrium oxide; metal carbides such as silicon carbide and aluminum carbide; metal nitride fillers such as silicon nitride and aluminum nitride; and inorganic fillers such as carbon black, aluminum fluoride, carbon fluoride, barium sulfate, silica, clay, and talc.

[0130] Among these, carbon black, aluminum oxide, yttrium oxide, silicon oxide, silicon carbide, polyimide, and carbon fluoride are preferred in terms of their shielding effect against various plasmas.

[0131] Furthermore, the inorganic fillers and organic fillers mentioned above may be used individually or in combination of two or more types.

[0132] The amount of filler added is preferably 0.5 to 100 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of the fluorine-containing polymer.

[0133] In fields where high purity and non-contamination are not particularly required, conventional additives that are incorporated into fluorine-containing polymer compositions, such as processing aids, plasticizers, and colorants, may be added as needed.

[0134] The composition may contain an organic basic compound. An example of an organic basic compound is a compound 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).

[0135] The compositions of this disclosure can be prepared by mixing the above-mentioned components using conventional polymer processing machinery, such as open rolls, Banbury mixers, and kneaders. Alternatively, they can also be prepared by using a closed-type mixer. The compositions of this disclosure can be suitably used as molding materials for obtaining molded articles by crosslinking.

[0136] 5. Molded products A molded article can be obtained by molding the composition of this disclosure. Furthermore, a molded article can be obtained by molding and crosslinking the composition of this disclosure.

[0137] One method for obtaining molded products from a composition is to first obtain a pre-molded body by molding the composition as a molding material, and then to crosslink the pre-molded body. The method for obtaining a pre-molded body from a composition 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, molded products can be obtained by heating and crosslinking with steam or the like after extrusion.

[0138] 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 170-200°C for 5-60 minutes. Any known crosslinking method can be used, such as press crosslinking.

[0139] Secondary crosslinking is preferably carried out at 180-320°C for 2-48 hours, and more preferably at 200-310°C for 5-24 hours. Temperature variations within this temperature range are also possible. Any known crosslinking method can be used, such as oven crosslinking.

[0140] The molded articles of this disclosure are obtained from the above composition. The molded articles of this disclosure preferably contain a triazine ring. The presence or absence of a triazine ring in the molded article can be confirmed by Fourier transform infrared spectroscopy (FT-IR).

[0141] In one embodiment, the molded article of the present disclosure is characterized by a high density of crosslinked structures formed by triazine rings. In one embodiment, the molded article of the present disclosure has a higher crosslink density than a molded article obtained from a composition containing the same amount of fluorine-containing polymer, the same amount of ammonia-generating compound, and the same amount of carrier (a carrier without the ammonia-generating compound). This is presumed to be because the composite particles contained in the composition of the present disclosure can efficiently generate ammonia.

[0142] The triazine ring content in the molded article is preferably 0.04 or more, and more preferably 0.05 or more. In this disclosure, the triazine ring content in the molded article is expressed as the ratio of the triazine ring content to the CF bond content in the molded article. The triazine ring content in the molded article can be measured by Fourier transform infrared spectroscopy (FT-IR). An infrared spectrum of the molded article is obtained using a Fourier transform infrared spectrophotometer (FT-IR), and the harmonic vibration peak of the CF bond appearing in the infrared spectrum (2360 cm⁻¹) is measured. -1 ) triazine ring peak (1525~1575cm) -1 The content of the triazine ring can be determined by calculating the absorbance ratio (A1555 / A2360) of the two compounds.

[0143] The molded articles of this disclosure can be suitably used as sealing materials for semiconductor manufacturing equipment that requires particularly high heat resistance, especially for semiconductor manufacturing equipment that undergoes high-density plasma irradiation. Examples of such sealing materials include O-rings, square rings, gaskets, packings, oil seals, bearing seals, lip seals, and the like.

[0144] 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.

[0145] 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:

[0146] (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 apparatus Oxidation diffusion device Ion implantation device

[0147] The molded articles of this disclosure exhibit excellent performance as sealing materials for, for example, CVD equipment, plasma etching equipment, reactive ion etching equipment, ashing equipment, or excimer laser exposure machines.

[0148] 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.

[0149] <1> According to the first aspect of this disclosure, A composition containing a fluorine-containing polymer and composite particles, The composite particles are composite particles in which an ammonia-generating compound is supported on a carrier. The carrier is at least one selected from the group consisting of silicon carbide, alumina, titania, silica, zirconia, ceria, silica-alumina, calcia, magnesia, and carbon black. The ammonia-generating compound is a compound that generates ammonia upon heating, is insoluble in perfluorohexane, and has a specific gravity lower than that of perfluorohexane at 20°C. A composition is provided. <2> According to the second aspect of this disclosure, A composition is provided in which, according to a first aspect, the amount of ammonia generated when the composite particles are heated at 180°C for 30 minutes is 1.1 times or more the amount of ammonia generated when only the ammonia-generating compound is heated at 180°C for 30 minutes. <3> According to the third aspect of this disclosure, A composition is provided in which the content of the ammonia-generating compound in the composite particles is 1% by mass or more, relative to the total mass of the ammonia-generating compound and the carrier, according to a first or second viewpoint. <4> According to the fourth aspect of this disclosure, A composition is provided in which the ammonia generation temperature of the composite particles is 70 to 300°C, according to any one of the first to third viewpoints. <5> According to the fifth aspect of this disclosure, A composition is provided in which the melting point of the ammonia-generating compound is 100 to 350°C, according to any one of the first to fourth viewpoints. <6> According to the sixth aspect of this disclosure, A composition is provided according to any one of the first to fifth aspects, wherein the ammonia-generating compound is at least one selected from urea, acetylurea, biuret, inorganic ammonium salts, N-phenylbenzamidine, and guanidines. <7> According to the seventh aspect of this disclosure, The BET specific surface area of ​​the carrier is 5 to 300 m². 2 A composition is provided that is / g according to any of the first to sixth aspects. <8> According to the eighth aspect of this disclosure, A composition is provided according to any one of the first to seventh views, wherein the content of the composite particles is 0.1 to 100 parts by mass per 100 parts by mass of the fluorine-containing polymer. <9> According to the ninth aspect of this disclosure, A composition is provided in which the fluorine-containing polymer is a fluorine-containing elastomer, according to any one of the first to eight aspects. <10> According to the tenth aspect of this disclosure, A composition is provided according to any one of the first to ninth aspects, wherein the fluorine-containing polymer is a fluorine-containing elastomer having a cyano group. <11> According to the eleventh aspect of this disclosure, A molded article is provided which is obtained from a composition according to any of the first to tenth aspects. [Examples]

[0150] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to such embodiments.

[0151] Preparation Example 1 In Preparation Example 1, silicon carbide particles with a particle size of approximately 2-3 μm were used as raw materials and supplied into a thermal plasma flame using a powder feeder. The input to the high-frequency oscillation coil for generating the thermal plasma flame was kept constant at 50 kW, and the internal pressure of the plasma torch was fixed at 40 kPa. Argon gas and hydrogen gas were used as the plasma gas, with the argon gas flow rate set to 210 liters / min (standard conditions) and the hydrogen gas flow rate to 15 liters / min (standard conditions). Argon gas was used as the cooling gas, with the argon gas flow rate set to 400 liters / min (standard conditions). Urea was used as the ammonia-generating compound, and water was used as the solvent. An aqueous solution containing urea (urea concentration 25.0 W / W%) was sprayed onto the primary silicon carbide particles using a spray gas from a region where the urea does not thermally decompose. Argon gas was used as the spray gas. The urea used was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0152] Preparation Example 2 In Preparation Example 2, silicon particles with a particle size of approximately 5 μm were used as raw materials and supplied into a thermal plasma flame using a powder feeder. The input to the high-frequency oscillation coil for generating the thermal plasma flame was kept constant at 30 kW, and the internal pressure of the plasma torch was fixed at 40 kPa. Argon and oxygen gases were used as plasma gases, with the argon gas flow rate set to 210 liters / min (converted to standard conditions) and the oxygen gas flow rate set to 5 liters / min (converted to standard conditions). Air was used as the cooling gas, with the air flow rate set to 600 liters / min (converted to standard conditions). Urea was used as the ammonia-generating compound, and water was used as the solvent. An aqueous solution containing urea (urea concentration 45.0 W / W%) was sprayed onto primary silicon oxide particles using a spray gas from a region where the urea does not thermally decompose. Argon gas was used as the spray gas. The urea used was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0153] Preparation Example 3 Preparation Example 3 was the same as Preparation Example 1, except that it used 2 / 3 the amount of silicon carbide particles with a particle size of approximately 2-3 μm as raw materials.

[0154] Preparation Example 4 In Preparation Example 4, the same procedure as in Preparation Example 1 was followed, except that two-thirds the amount of silicon carbide particles with a particle size of approximately 2-3 μm was used as the raw material, and methane gas was added to the argon gas used as the cooling gas, with the methane gas flow rate set to 0.5 liters / minute.

[0155] The numerical values ​​for each example and comparative example were measured by the following method.

[0156] (Composition of perfluoroelastomers) 19 This was determined by F-NMR analysis.

[0157] (Mooney viscosity of perfluoroelastomer) The viscosity was measured using an ALPHA TECHNOLOGIES MV2000E Mooney viscometer at 170°C or 100°C, in accordance with JIS K6300.

[0158] (Crosslinking properties) The crosslinking properties of rubber compositions were measured using an ALPHA TECHNOLOGIES RPA-2000 rubber processability tester under conditions of 180°C for 30 minutes. In the crosslinking properties, G'max represents the maximum storage modulus, G'min represents the minimum storage modulus, ΔG' represents the difference between the maximum and minimum storage modulus, and T90 represents the optimal crosslinking time.

[0159] (Normal physical properties) In accordance with JIS K6251, the tensile strength (MPa), 100% tensile stress (MPa), and elongation (%) of a 2mm thick molded product were measured at normal conditions (25°C).

[0160] (Hardness (ShoreA) Peak) The hardness (Shore A) was measured (peak value) of a molded product with a thickness of 2 mm in accordance with JIS K6253.

[0161] (Compression set) The compression set rate was measured in accordance with the method described in ASTM D395 or JIS K6262. The O-rings prepared in the examples and comparative examples were compressed to a compression rate of 25% at room temperature using a compression device (an O-ring with a thickness (wire diameter) of 3.5 mm was compressed to a thickness of 2.625 mm). Next, the compression device with the compressed O-ring fixed was placed stationary in an electric furnace, left for 70 hours at 300 °C, and then the compression device was taken out of the electric furnace. The O-ring was removed from the compression device, and the removed O-ring was placed stationary in a constant temperature chamber and left for 30 minutes at 23 °C, and the thickness (t2) of the O-ring was measured. The compression set rate was determined by the following formula. Compression set rate (%) = (t0 - t2) / (t0 - t1) × 100 t0: Original thickness of the O-ring (mm) t1: Thickness of the spacer (mm) t2: Thickness of the O-ring after the compression test (mm) In the above test, t0 = 3.5 mm and t1 = 2.625 mm.

[0162] The following materials were used in the examples and comparative examples.

[0163] Fluorine-containing elastomer (perfluoroelastomer) Composition: TFE / PMVE / CF2=CFOCF2CF(CF3)OCF2CF2CN = 59.4 / 40.1 / 0.5 (mol%) Mooney viscosity (ML1+20(170 °C)): 80

[0164] MT carbon (manufactured by Cancarb, Thermax N990) Urea (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) SiC, Si particles A: (manufactured by Nisshin Engineering Co., Ltd., 10041, bulk density 0.08 g / cm 3 ) SiC, Si particles B: (manufactured by Nisshin Engineering Co., Ltd., 02071, bulk density 0.11 g / cm 3 ) SiO2 particles A: (Manufactured by Nisshin Engineering Co., Ltd., 10071, bulk density 0.06 g / cm³) 3 ) SiC particles A: (Manufactured by Nisshin Engineering Co., Ltd., 02271, bulk density 0.30 g / cm³) 3 )

[0165] Composite particle 1: Composite particles prepared in Preparation Example 1 (mass ratio [urea / (silicon carbide + silicon)] = 0.3 / 1.8) Composite particle 2: Composite particles prepared in Preparation Example 2 (mass ratio (urea / silicon oxide) = 0.3 / 2.3) Composite particle 3: Composite particles prepared in Preparation Example 3 (mass ratio [urea / (silicon carbide + silicon)] = 0.3 / 2.6) Composite particle 4: Composite particles prepared in Preparation Example 4 (mass ratio (urea / silicon carbide) = 0.3 / 1.9)

[0166] The content of each component in composite particles 1, 3, and 4 was determined by Rietveld analysis. Aeris analyzer from Spectris was used for the Rietveld analysis. The urea content of composite particle 2 was calculated using a Hitachi High-Tech Science STA7200 differential thermogravimetric analyzer. Primary silicon dioxide particles and composite particle 2 were heated in air at 10°C / min to 600°C, and the value at which the weight decreased the most was determined and calculated using the following method. Urea content of composite particle 2 = BA A: Maximum weight loss of primary silicon dioxide particles before spraying the urea-containing aqueous solution. B: Maximum weight reduction rate of composite particles 2 after spraying an aqueous solution containing urea

[0167] Crosslinking agent: 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[N1-phenyl-1,2-benzenediamine]

[0168] Example 1 A fluorine-containing elastomer composition was prepared by mixing 100 parts by mass of fluorine-containing elastomer with 23 parts by mass of MT carbon and 2.1 parts by mass of the composite particles (composite particle 1) obtained in Preparation Example 1, and kneading the mixture in an open roll. The crosslinking properties of the obtained fluorine-containing elastomer composition were measured using an ALPHA TECHNOLOGIES RPA-2000 rubber processability tester. The results are shown in Table 1.

[0169] Example 2 A fluorine-containing elastomer composition was prepared in the same manner as in Example 1, except that 2.6 parts by mass of composite particles (composite particles 2) obtained in Preparation Example 2 were used instead of 2.1 parts by mass of composite particles (composite particles 1) obtained in Preparation Example 1, and the crosslinking properties were measured. The results are shown in Table 1.

[0170] Comparative Example 1 A fluorine-containing elastomer composition was prepared in the same manner as in Example 1, except that 1.8 parts by mass of SiC,Si particles A and 0.3 parts by mass of urea were used instead of 2.1 parts by mass of the composite particles (composite particle 1) obtained in Preparation Example 1, and the crosslinking properties were measured. The results are shown in Table 1.

[0171] Comparative Example 2 A fluorine-containing elastomer composition was prepared in the same manner as in Example 1, except that 2.3 parts by mass of SiO2 particles A and 0.3 parts by mass of urea were used instead of 2.1 parts by mass of the composite particles (composite particle 1) obtained in Preparation Example 1, and the crosslinking properties were measured. The results are shown in Table 1.

[0172] Examples 3-5, Comparative Examples 3-5 A fluorine-containing elastomer composition was prepared in the same manner as in Example 1, except that the compound composition was changed as shown in Tables 2 and 3, and the crosslinking properties were measured. The results are shown in Tables 2 and 3.

[0173] The obtained fluorine-containing elastomer composition was pressed at 180 °C for 30 minutes for crosslinking, and then oven crosslinked at 200 °C for 12 hours, 250 °C for 3 hours, and 290 °C for 3 hours in an oven to produce a molded product with a thickness of 2 mm and an O-ring of P24 size. The physical properties of the obtained molded product were measured, and the compression set rate of the O-ring was measured. The results are shown in Tables 2 to 3.

[0174]

Table 1

[0175]

Table 2

[0176]

Table 3

[0177] The compositions of Example 1 and Comparative Example 1 contain the same amount of urea and the same amount of SiC and Si components. It can be seen that the composition of Example 1 using composite particles in which urea is supported on SiC and Si particles (silicon carbide particles) has a shorter optimum crosslinking time (T90) than the composition of Comparative Example 1, and the fluorine-containing polymer can be crosslinked in a shorter time. Also, it can be seen that the molded product obtained from the composition of Example 3 using composite particles in which urea is supported on SiC and Si particles (silicon carbide particles) has a smaller compression set than the molded product obtained from the composition of Comparative Example 3.

[0178] Such an effect obtained by blending composite particles in which an ammonia-generating compound is supported on a carrier into a fluorine-containing polymer can also be grasped by comparing Example 2 with Comparative Example 2, Example 4 with Comparative Example 4, and Example 5 with Comparative Example 5.

Claims

1. A composition containing a fluorine-containing polymer and composite particles, The composite particles are composite particles in which an ammonia-generating compound is supported on a carrier. The carrier is at least one selected from the group consisting of silicon carbide, alumina, titania, silica, zirconia, ceria, silica-alumina, calcia, magnesia, and carbon black. The ammonia-generating compound is a compound that generates ammonia upon heating, is insoluble in perfluorohexane, and has a specific gravity lower than that of perfluorohexane at 20°C. composition.

2. The composition according to claim 1, wherein the amount of ammonia generated when the composite particles are heated at 180°C for 30 minutes is 1.1 times or more the amount of ammonia generated when only the ammonia generating compound is heated at 180°C for 30 minutes.

3. The composition according to claim 1 or 2, wherein the content of the ammonia-generating compound in the composite particles is 1% by mass or more with respect to the total mass of the ammonia-generating compound and the carrier.

4. The composition according to claim 1 or 2, wherein the ammonia generation temperature of the composite particles is 70 to 300°C.

5. The composition according to claim 1 or 2, wherein the melting point of the ammonia-generating compound is 100 to 350°C.

6. The composition according to claim 1 or 2, wherein the ammonia-generating compound is at least one selected from urea, acetylurea, biuret, inorganic ammonium salts, N-phenylbenzamidine, and guanidines.

7. The BET specific surface area of ​​the carrier is 5 to 300 m². ２ The composition according to claim 1 or 2, wherein the amount is / g.

8. The composition according to claim 1 or 2, wherein the content of the composite particles is 0.1 to 100 parts by mass per 100 parts by mass of the fluorine-containing polymer.

9. The composition according to claim 1 or 2, wherein the fluorine-containing polymer is a fluorine-containing elastomer.

10. The composition according to claim 1 or 2, wherein the fluorine-containing polymer is a fluorine-containing elastomer having a cyano group.

11. A molded article obtained from the composition according to claim 1 or 2.

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