Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine

Definitions

• the present invention relates to a method for producing a solid composition, a solid composition, and a crosslinked rubber article.
• Crosslinked rubber articles obtained by crosslinking a composition containing a fluorine-containing polymer are used in various industrial fields because of their excellent heat resistance, chemical resistance, flame retardancy, weather resistance, etc.
• methods for producing such fluorine-containing polymers include a method in which a fluorine-containing monomer is emulsion-polymerized in an aqueous medium using an emulsifier (see Patent Document 1).
• the specific monomer is a monomer including TFE and PAVE.
• the preferred embodiments of TFE and PAVE as the specific monomer are the same as the preferred embodiments of TFE and PAVE in the first fluorine-containing polymer described above.
• the total amount of TFE and PAVE used is preferably from 80 to 100 mol %, more preferably from 90 to 100 mol %, and even more preferably from 95 to 100 mol %, based on the amount of the specific monomer used.
• R 41 represents a divalent perfluorohydrocarbon group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom at the end or between carbon-carbon bonds of a divalent perfluorohydrocarbon group having 1 to 10 carbon atoms.
• a more preferred specific example of the monomer is CH 2 ⁇ CH(CF 2 ) 6 CH ⁇ CH 2 (hereinafter, also referred to as "C6DV").
• BO is preferably C3DVE or C4DVE.
• R Hal examples include a monomer having a bromine atom and a monomer having an iodine atom.
• monomers having a bromine atom include CF 2 ⁇ CFOCF 2 CF 2 CF 2 OCF 2 CF 2 Br, bromotrifluoroethylene, 4-bromo-3,3,4,4-tetrafluorobutene-1 (BTFB), vinyl bromide, 1-bromo-2,2-difluoroethylene, perfluoroallyl bromide, 4-bromo-1,1,2-trifluorobutene-1, 4-bromo-1,1,3,3,4,4-hexafluorobutene, 4-bromo-3-chloro-1,1,3,4,4-pentafluorobutene, 6-bromo-5,5,6,6-tetrafluorohexene, and 4-bromoperfluorobutene-1,3,3-difluoroallyl bromide.
• fluorinated compounds such as 2-bromo-perfluoroethyl perfluorovinyl ether and CF 2 Br-R f -O-CF ⁇ CF 2
• R f is a perfluoroalkylene group
• fluorovinyl ethers such as CF 2 BrCF 2 O-CF ⁇ CF 2 , ROCF ⁇ CFBr, and ROCBr ⁇ CF 2
• R is a lower alkyl group or a fluoroalkyl group
• CH 3 OCF ⁇ CFBr and CF 3 CH 2 OCF ⁇ CFBr specifically, CH 3 OCF ⁇ CFBr and CF 3 CH 2 OCF ⁇ CFBr.
• R CN preferably has a polymerizable unsaturated bond, and more preferably has one polymerizable unsaturated bond.
• Specific examples of the polymerizable unsaturated bond include a carbon atom-carbon atom double bond (C ⁇ C) and a carbon atom-carbon atom triple bond (C ⁇ C).
• R CN is preferably a monomer represented by the following formula (5) in that the solid composition has better releasability and heat resistance.
• CR 51 R 52 CR 53 -R 54 -CN (5)
• R 51 , R 52 , and R 53 each independently represent a hydrogen atom, a fluorine atom, or a methyl group
• R 54 represents a divalent perfluorohydrocarbon group having 1 to 10 carbon atoms, or a group having an ethereal oxygen atom at the end or between carbon-carbon bonds of a divalent perfluorohydrocarbon group having 1 to 10 carbon atoms.
• the perfluoroalkyl group may be linear or branched.
• the number of carbon atoms in R f2 is preferably 1 to 3.
• n is 0, m is preferably 1 or 2.
• n is 1, m is preferably an integer of 2 to 4.
• n is 2 or 3, m is preferably 0.
• n is preferably an integer of 1 to 3.
• the amount of other monomers used is preferably 0 to 20 mol %, more preferably 0 to 10 mol %, and even more preferably 0 to 5 mol %, relative to the amount of the specific monomer used.
• the specific monomer preferably consists of only TFE and PAVE, or contains TFE and PAVE, and also contains at least one monomer selected from the group consisting of BO, R Hal , and R CN .
• the specific monomer is preferably polymerized in the presence of a polymerization initiator.
• the polymerization initiator is preferably an oil-soluble radical initiator, a water-soluble radical initiator, or a water-soluble oxidation-reduction catalyst.
• oil-soluble radical initiators include oil-soluble organic peroxides such as tert-butyl peroxypivalate and diisopropyl peroxydicarbonate.
• the water-soluble radical initiator include persulfates such as ammonium persulfate and potassium persulfate, water-soluble organic peroxides such as disuccinic acid peroxide, bisglutaric acid peroxide, and tert-butyl hydroperoxide.
• persulfates such as ammonium persulfate and potassium persulfate
• water-soluble organic peroxides such as disuccinic acid peroxide, bisglutaric acid peroxide, and tert-butyl hydroperoxide.
• an oxidizing agent such as bromic acid or its salt, chloric acid or its salt, persulfuric acid or its salt, permanganic acid or its salt, or hydrogen peroxide
• a reducing agent such as sulfurous acid or its salt, hydrogen sulfite or its salt, thiosulfuric acid or its salt, organic acid, or inorganic salt.
• persulfate potassium persulfate or ammonium persulfate is preferred.
• sulfite sodium sulfite is preferred.
• inorganic salt a combination of sulfate anion, sulfite anion, or chloride anion and metal ion is preferred.
• metal ion a transition metal is preferred, and manganese, iron, cobalt, nickel, copper, zinc, cerium, and silver ions are preferred, and iron ion is preferred.
• iron (II) sulfate is preferred.
• the polymerization initiator is preferably an oil-soluble radical initiator or a water-soluble radical initiator, more preferably a water-soluble radical initiator from the viewpoint of more efficient production of the fluorine-containing polymer, and further preferably a persulfate or a water-soluble organic peroxide. Two or more types of polymerization initiators may be used in combination.
• the chain transfer agent having an iodine atom is preferably a compound represented by formula (I). (R f )-(X) 2 (I)
• R f is a fluoroalkylene group having 1 to 16 carbon atoms or an aromatic ring group
• X is an iodine atom or a bromine atom, and at least one X is an iodine atom.
• the fluoroalkylene group of Rf may be linear or branched.
• Rf is preferably a perfluoroalkylene group. It is preferable that all of X's are iodine atoms.
• the compound represented by formula (I) include 1,2-diiodoperfluoroethane, 1,3-diiodoperfluoropropane, 1,4-diiodoperfluorobutane (hereinafter also referred to as "C4DI"), 1,5-diiodoperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorocutane, 1,3-diiodo-2-chloroperfluoropropane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2-diiodoperfluoroethane, 1,3-diiodoperfluoroethane, 1,4
• iodoethane examples include iodoethane, 1,3-diiodo-n-propane, (2-iodoethyl)-substituted benzene, 1-iodo-4-bromoperfluorobutane, 1-iodo-6-bromoperfluorohexane, 1-iodo-8-bromoperfluoroctane, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodo monobromo-substituted benzene, and diiodo monobromo-substituted benzene.
• the amount of the chain transfer agent used is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of the specific monomer used.
• the specific monomer contains at least one monomer selected from the group consisting of BO, R Hal and R CN , or the first aqueous dispersion contains a chain transfer agent containing an iodine atom.
• the polymerization temperature is preferably from 10 to 95°C, more preferably from 15 to 90°C.
• the polymerization pressure is preferably from 0.5 to 4.0 MPaG, more preferably from 0.6 to 3.5 MPaG.
• the polymerization time is preferably from 90 to 1,000 minutes, more preferably from 90 to 700 minutes.
• the polymerization of the specific monomer is preferably carried out in the substantial absence of an emulsifier.
• the emulsifier may be any of the emulsifiers described above. "Substantially no emulsifier is present" means an environment in which the content of emulsifier is 0.03 ppm by mass or less relative to the total mass of the aqueous medium contained in the first aqueous dispersion, preferably 0.02 ppm by mass or less, and more preferably 0 ppm by mass.
• the amount of PAVE units is 15 to 95 mol%, preferably 20 to 60 mol%, and from the viewpoint of more efficient production of the second fluorine-containing polymer, more preferably 25 to 50 mol%, further preferably 30 to 40 mol% based on the total amount of TFE units and PAVE units.
• PMVE units or PPVE units are used as the PAVE units, the suitable amount is similar.
• the total content of TFE units and PAVE units in the second fluorinated polymer is preferably from 80 to 100 mol %, more preferably from 90 to 100 mol %, and even more preferably from 95 to 100 mol %, based on all units of the second fluorinated polymer.
• the second fluorine-containing polymer contains TFE units and PAVE units, and also preferably contains units based on other monomers. Examples of the units based on other monomers include the units based on other monomers in the above-mentioned specific monomers.
• the TFE unit is preferably from 35 to 80 mol %, more preferably from 47 to 75 mol %, and even more preferably from 59 to 70 mol %, based on all units.
• the amount of PAVE units relative to all units is preferably from 20 to 60 mol %, more preferably from 25 to 50 mol %, and even more preferably from 30 to 40 mol %.
• the amount of units based on other monomers is preferably from 0.01 to 5 mol %, more preferably from 0.05 to 3 mol %, and even more preferably from 0.10 to 1 mol %, based on all units.
• the second fluorine-containing polymer preferably contains at least one selected from the group consisting of a polymerizable unsaturated bond, a chlorine atom, a bromine atom, an iodine atom, and a nitrile group, and more preferably contains at least one selected from the group consisting of a polymerizable unsaturated bond, an iodine atom, and a nitrile group, in that the crosslinkability of the solid composition is more excellent.
• the second fluorine-containing polymer contains at least one type selected from the above at at least one of its terminals and side chains.
• step 1 a second fluoropolymer is produced, and a second aqueous dispersion is obtained in which particles containing the second fluoropolymer are dispersed in an aqueous medium.
• the second aqueous dispersion is an aqueous dispersion containing the second fluoropolymer obtained in step 1.
• the second aqueous dispersion is an aqueous dispersion in which particles containing a fluoropolymer (hereinafter also referred to as "specific particles") are dispersed in an aqueous medium, and the fluoropolymer contains the second fluoropolymer.
• the specific particles may or may not contain the first fluorine-containing polymer.
• the second aqueous dispersion may contain the first fluoropolymer dispersed in the form of particles.
• the content of the specific particles in the second aqueous dispersion is preferably 1 to 50 mass%, more preferably 10 to 40 mass%, and even more preferably 15 to 30 mass%, relative to the total mass of the second aqueous dispersion, from the viewpoint of dispersion stability of the specific particles.
• the average particle size of the specific particles is preferably 1 ⁇ m or less, and from the viewpoint of the dispersion stability of the specific particles, is more preferably 500 nm or less, and further preferably 400 nm or less.
• the average particle size of the specific particles is preferably 50 nm or more, more preferably 60 nm or more, and even more preferably 80 nm or more, from the viewpoint of recovery efficiency in step 2 described below.
• the average particle size of the specific particles is a particle size calculated by analyzing an autocorrelation function obtained by dynamic light scattering using a monodisperse cumulant method.
• aqueous medium contained in the second aqueous dispersion are the same as the specific examples of the aqueous medium contained in the first aqueous dispersion described above.
• the content of the aqueous medium is preferably 50 to 99 mass %, more preferably 60 to 99 mass %, and even more preferably 70 to 99 mass %, based on the total mass of the second aqueous dispersion, from the viewpoint of dispersion stability of the specific particles.
• the content of the emulsifier in the second aqueous dispersion is preferably 100 mass ppm or less, more preferably 75 mass ppm or less, even more preferably 50 mass ppm or less, even more preferably 1 mass ppm or less, and particularly preferably 25 mass ppb or less, based on the total mass of the second aqueous dispersion, in order to obtain a better effect of the present invention. It is also preferable that the content is less than the quantification limit of the measurement method in the examples. The lower limit is 1 mass ppb. It is preferable that no emulsifier is used in the second aqueous dispersion.
• the content of the emulsifier can be measured by the same method as that for the first aqueous dispersion described above. Specific examples of the emulsifier are as described above.
• the emulsifier in the second aqueous dispersion may or may not be water-soluble.
• step 2 of this production method the second aqueous dispersion obtained in step 1 is subjected to a stirring treatment, and a solid matter is recovered to obtain a solid composition.
• a specific example of the stirring method is a method using a stirring device that rotates a stirring shaft equipped with stirring blades.
• Specific examples of the shape of the stirring blade include paddle blades, inclined paddle blades, propeller blades, disk blades, three-blade swept-back blades, anchor blades, turbine blades, and disk turbine blades, with paddle blades and disk turbine blades being preferred in terms of excellent stirring efficiency.
• the number of the stirring blades is preferably 1 to 10, and more preferably 2 to 4.
• the stirring device may be provided with a baffle plate.
• the stirring time is preferably from 0.1 to 24 hours, more preferably from 0.1 to 12 hours, and even more preferably from 0.1 to 6 hours.
• the peripheral speed of stirring is preferably 2 to 50 m/s, more preferably 3 to 30 m/s, and even more preferably 5 to 30 m/s.
• the peripheral speed may be constant during stirring or may change during stirring. It is also preferable that the peripheral speed is faster than the peripheral speed in step 1.
• the peripheral speed of stirring refers to the speed of the blade at the tip of the blade.
• the temperature of the aqueous dispersion during the stirring treatment is preferably from 10 to 90°C, more preferably from 10 to 80°C, and even more preferably from 15 to 70°C.
• Solid matter is a solid matter obtained by the above stirring treatment, and contains a fluoropolymer.
• solid matter refers to a solid that is not stably dispersed in an aqueous medium, and a dispersoid that is stably dispersed in an aqueous medium is considered not to be a solid matter even if it is a solid that is insoluble in the aqueous medium.
• the insoluble components e.g., specific particles
• the dispersoid that is stably dispersed in the aqueous medium is not included in the solid matter, and the precipitate and the floating matter are included in the solid matter.
• the above-mentioned solid matter may be, for example, an aggregate of specific particles.
• the above-mentioned stably dispersed dispersoid is, for example, a dispersoid that passes through a type 5A filter paper as specified in JIS P 3801 [filter paper (for chemical analysis)].
• the solid material is recovered to obtain the solid composition of the present invention.
• Exemplary methods for recovering solids include filtration and centrifugation, with filtration being preferred.
• the present production method further includes a step of washing the recovered solid composition (hereinafter also referred to as "step 3").
• step 3 components other than the fluoropolymer contained in the solid composition (e.g., emulsifier, monomer, polymerization initiator, and reactants thereof) can be removed, making it easier to obtain a crosslinked rubber article having desired physical properties.
• the washing liquid in the washing step may be the above-mentioned aqueous medium, and is preferably water, more preferably ultrapure water, since it contains a small amount of impurities that may cause crosslinking inhibition.
• washing method include a method of immersing the solid composition in a washing liquid and stirring it, and a method of showering the washing liquid onto the solid composition. Washing and dehydration of the solid composition may be repeated multiple times. Specific examples of the dehydration method include squeezing and centrifugation.
• the amount of the washing liquid in the washing step is preferably 1 to 20 times, more preferably 1 to 10 times, and even more preferably 1 to 5 times, the total mass of the solid composition.
• the temperature of the washing solution in the washing step is preferably from 5 to 80°C, more preferably from 10 to 70°C, and even more preferably from 20 to 60°C.
• Solid composition The process results in a solid composition.
• the solid composition of the present invention (hereinafter also referred to as “the present solid composition”) contains a fluoropolymer containing TFE units and PAVE units, is substantially free of an emulsifier, and satisfies the requirement X described below.
• the fluorine-containing polymer contained in the present solid composition contains TFE units and PAVE units.
• the details of the TFE unit and the PAVE unit are the same as those of the TFE unit and the PAVE unit in the above-mentioned first fluorine-containing polymer, respectively, and preferred embodiments are also the same.
• the fluoropolymer contained in the present solid composition preferably contains a second fluoropolymer, and more preferably is the second fluoropolymer. That is, a preferred embodiment of the fluoropolymer contained in the present solid composition is the same as the above-mentioned second fluoropolymer.
• the solid composition may or may not contain a first fluoropolymer.
• all units of the fluorine-containing polymer means all units contained in that one type of fluorine-containing polymer, and when there are two or more types of fluorine-containing polymers contained in the specific particles, "all units of the fluorine-containing polymer” means all units contained in the two or more types of fluorine-containing polymers.
• the fluorine-containing polymer contained in this solid composition may contain units based on other monomers other than TFE units and PAVE units. For example, units based on other monomers in the specific monomers mentioned above can be mentioned.
• the solid composition preferably does not substantially contain a compound (emulsifier) represented by any one of formulas (S1) to (S4). If no emulsifier is used during the production of the first fluorine-containing polymer contained in the first aqueous dispersion, the amount of the compound represented by any one of formulas (S1) to (S4) generated can be suppressed, making it easier to adjust the content of these compounds.
• a compound (emulsifier) represented by any one of formulas (S1) to (S4) can be suppressed, making it easier to adjust the content of these compounds.
• n1 is an integer from 3 to 19
• n2 is an integer from 4 to 20
• Each M is independently a hydrogen atom, Na, K, or NH4 .
• the total content of the compounds represented by any one of formulas (S1) to (S4) is preferably 25 mass ppb or less, more preferably 20 mass ppb or less, based on the total mass of the solid composition. It is also preferably equal to or less than the quantification limit of the measurement method in the examples. The lower limit may be more than 0 mass ppb.
• TFE and PMVE were injected until the pressure of the reactor reached 1.5 MPa [gauge], and an aqueous solution of ammonium persulfate (APS aqueous solution, 1.0 mass%, 20 ml, ammonium persulfate was 0.2 g) was added to start polymerization. Since the pressure in the reactor decreased with the start of polymerization, TFE/PMVE was injected at 65/35 (molar ratio) to keep the pressure constant. When 256 g of TFE and 217 g of PMVE were injected, the reactor was cooled to terminate the polymerization reaction. The polymerization time was 380 minutes. The total amount of monomers added before the start of polymerization was 14 g of TFE and 90 g of PMVE. The total amounts of the monomers added after the initiation of polymerization were 256 g of TFE and 217 g of PMVE. The total amount of TFE added was 270 g, and the total amount of PMVE added was 307 g.
• the solid content of the aqueous dispersion 1-1 was measured, and an amount of the aqueous dispersion 1-1 equivalent to 0.05 g of solid content was weighed into a 100 mL screw tube. Then, water and methanol were added to the weighed aqueous dispersion 1-1 so that the water/methanol ratio was 40 g, 50/50 volume %. Then, the mixture was shaken well until coagulation occurred. The solid content was removed, and the liquid phase was centrifuged at 4000 rpm for 1 hour to extract the supernatant. As a result, the content of the compound represented by any one of formulas (S1) to (S4) was also below the quantification limit for the aqueous dispersion 1-1.
• Aqueous Dispersion 2-1 was a dispersion in which particles (average particle size 92.7 nm) containing a fluoropolymer were dispersed in an aqueous medium, and had a solid content concentration of 20.5% by mass.
• the aqueous dispersion 2-1 was placed in a cylindrical tank and stirred at 5 m/s for 150 minutes using a disk turbine impeller with eight blades attached at right angles at equal intervals to the outer periphery of a disk, and the solid matter was then collected by filtration.
• the collected solid matter was washed with 2,000 g of ultrapure water at 40°C and dried to obtain a rubber-like solid composition 1.
• the peripheral speed of stirring (m/s) is the speed of the impeller at the tip of the impeller.
• the fluorine-containing polymer contained in the obtained solid composition 1 was analyzed by NMR, and as a result, it was found that the ratio of PAVE units to TFE units was 34/66 (molar ratio).
• Raw material liquid D was produced in the same manner as raw material liquid B, except that raw material liquid C was used instead of raw material liquid A.
• Raw material liquid D contained particles of fluoropolymer 1C dispersed in an aqueous medium, and the content of fluoropolymer 1C was 0.6% by mass based on the total mass of raw material liquid D.
• Example 3 A stainless steel pressure reactor having an internal volume of 2.2 L and equipped with an anchor impeller was charged with raw material liquid D (1000 g) and ultrapure water (175 g) to obtain aqueous dispersion 1-3.
• the content of fluoropolymer 1C was 0.4 mass% based on the total mass of aqueous dispersion 1-3.
• Aqueous dispersion 1-3 did not substantially contain a water-soluble emulsifier. The content of the emulsifier was confirmed by the same method as for aqueous dispersion 1-1 described above.
• PMVE (72 g) and TFE (14 g) were charged into the aqueous dispersion 1-3, and the temperature was raised to 80° C.
• the aqueous dispersion 2-3 was stirred with six turbine blades at 30 m/s for 150 minutes, and then the solid matter was collected by filtration.
• the collected solid matter was washed with 2,000 g of ultrapure water at 25° C. and dried to obtain a rubber-like solid composition 3.
• the fluorine-containing polymer contained in the obtained solid composition 3 was analyzed by NMR, and as a result, it was found that the ratio of PAVE units to TFE units was 34/65 (molar ratio).
• Aqueous Dispersion 4 was a dispersion in which particles (average particle size: 84 nm) containing a fluoropolymer were dispersed in an aqueous medium, and had a solids concentration of 21.1% by mass.
• An aqueous aluminum sulfate solution (5%, 2,000 g) was added to the aqueous dispersion 4, and the aggregate was collected by filtration.
• the collected aggregate was washed with 2,000 g of ultrapure water at 40° C., and then the solid was collected by filtration.
• the collected solid was dried to obtain a rubber-like solid composition 4.
• the fluorine-containing polymer contained in the obtained solid composition 4 was analyzed by NMR, and as a result, it was found that the ratio of PAVE units to TFE units was 35/65 (molar ratio).
• Example 5 After degassing a stainless steel pressure reactor with an internal volume of 2.2 L equipped with an anchor blade, ultrapure water (1004 g), a 30% by weight solution (80.1 g) of C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4 (emulsifier A) as an emulsifier, and a 5% by weight aqueous solution (10.49 g) of disodium hydrogen phosphate 12-hydrate were charged, and the gas phase was replaced with nitrogen. While stirring at a speed of 600 rpm using an anchor blade, PMVE (72 g) and TFE (14 g) were pressed into the vessel, and the internal temperature was raised to 80° C.
• emulsifier A C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4
• Aqueous Dispersion 5 was a dispersion in which particles (average particle diameter: 98.6 nm) containing the fluoropolymer 1G were dispersed in an aqueous medium, and had a solid content concentration of 20.1% by mass.
• the aqueous dispersion 5 was added to an aqueous nitric acid solution (3% by mass, 2,500 g) and stirred, and the solid matter was collected by filtration.
• the collected solid matter was washed with 2,000 g of ultrapure water at 60° C. and dried to obtain a rubber-like solid composition 5.
• the fluorine-containing polymer contained in the obtained solid composition 5 was analyzed by NMR, and as a result, it was found that the ratio of PAVE units to TFE units was 35/65 (molar ratio).
• CB MT Carbon N990, manufactured by Vanderbilt Crosslinking aid: TAIC-WH60, manufactured by Mitsubishi Chemical, triallyl isocyanurate 60% silica dilution Crosslinking agent: Perhexa 25B, manufactured by NOF Corp., 2,5-dimethyl-2.5-di(t-butylperoxy)hexane Release agent: Nonsal SN-1, manufactured by NOF Corp., sodium stearate
• the obtained crosslinking rate evaluation sheet was cut into 10 g to obtain a cut sheet.
• the cut sheet was sandwiched between two polyester films (ALFA Technologies, PART#F0311-S, 130 mm x 130 mm x 24 ⁇ m) from both sides of the main surface to obtain a measurement sample.
• the torque (dNm) was measured under the following conditions: measuring device: PREMIER RPA (manufactured by Alpha Technologies), die shape: D0380, 150 ° C., 12 minutes, 100 cpm, angle: 3.00 deg.
• the minimum value of the obtained torque was set to 0%, and the maximum value of the torque was set to 100%, and the processing time at which the torque value reached 50% was set to t 50 , and the processing time at which the torque value reached 90% was set to t 90 .
• the obtained extract was measured by LC/MS/MS.
• the emulsifier having a fluorine atom and the hydrocarbon emulsifier in the extract were measured using a liquid chromatograph mass spectrometer. The measurement equipment configuration and LC-MS measurement conditions are shown in Table 1. Using aqueous solutions of an emulsifier having a fluorine atom and a hydrocarbon emulsifier with known concentrations, aqueous solutions with five or more levels of content were prepared, and LC/MS analysis was performed on the aqueous solutions with each content.
• the relationship between the content and the area area relative to the content was plotted, and a calibration curve was drawn. Using the above calibration curve, the area area of the LC/MS chromatogram of the emulsifier having a fluorine atom and the hydrocarbon emulsifier in the extract was converted to the content of the emulsifier having a fluorine atom and the hydrocarbon emulsifier.
• the MRM measurement parameters are appropriately selected according to the structures of the emulsifier having a fluorine atom and the hydrocarbon emulsifier to be measured.
• the MRM parameters may be those from literature or may be calculated by an LC-MS device.
• the specific procedure for determining the MRM parameters by an LC-MS device is as follows. Using an LC/MS device (Shimadzu Corporation, LCMS-8060NX), select the search for product ions, input the molecular weights of the emulsifier having a fluorine atom and the hydrocarbon emulsifier to be measured, and perform precursor ion, precursor adjustment, voltage optimization, and product m/z optimization.
• the calculated MRM measurement parameters are used.
• the MRM measurement parameters for compounds (S2) and (S4) which are emulsifiers having a fluorine atom, are shown in the table below.
• MS represents a hydrogen atom, a metal atom, NR4 (wherein R may be the same or different and represents a hydrogen atom or an organic group having 1 to 10 carbon atoms), an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a phosphonium which may have a substituent.
• F-(CF2)n2-SO3MS (S4)
• n1 is an integer from 3 to 17
• n2 is an integer from 4 to 12.

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