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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
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  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08K3/28—Nitrogen-containing compounds
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
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  • C08K5/00—Use of organic ingredients
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
  • C08K5/57—Organo-tin compounds
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
  • C09K3/1009—Fluorinated polymers, e.g. PTFE
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  • 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
  • C08F214/26—Tetrafluoroethene
  • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
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  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/006—Additives being defined by their surface area
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  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2003/1034—Materials or components characterised by specific properties
  • C09K2003/1068—Crosslinkable materials

Definitions

• the present disclosure relates to a composition, a crosslinked product, and a sealing material.
• Perfluoroelastomer is used as a material for sealing materials because it has excellent sealing properties and heat resistance. Since plasma resistance is required for sealing materials used in semiconductor manufacturing equipment, a technique is known in which a filler is added to a perfluoroelastomer to impart plasma resistance to the sealing material.
• Patent Document 1 describes a crosslinkable elastomer composition comprising a crosslinkable elastomer and a non-oxide ceramic such as a carbide or a nitride.
• Patent Document 2 describes a crosslinkable fluoroelastomer composition containing a crosslinkable fluoroelastomer and silicon carbide particles having a bulk density of 0.15 g/cm 3 or less.
• the present disclosure aims to provide a composition capable of obtaining a crosslinked product having excellent plasma resistance and excellent compression set resistance.
• composition containing a perfluoroelastomer and a filler wherein the filler contains silicon carbide and graphite, and wherein the filler contains silicon carbide and graphite, and the A composition in which the ratio of the area (C) of the peak derived from the graphite in the filler to the area (SiC) of the peak derived from silicon carbide (area (C)/area (SiC)) is 0.7 or more. things are provided.
• the BET specific surface area of the filler determined by a nitrogen adsorption method is preferably 15 to 200 m 2 /g.
• the ratio of the BET specific surface area of the filler determined by the water vapor adsorption method to the BET specific surface area of the filler determined by the nitrogen adsorption method is preferably 1 to 60%.
• the filler has a bulk density of 0.10 g/cm 3 or more.
• the content of the filler is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the perfluoroelastomer. It is preferable that the composition of the present disclosure further contains at least one selected from the group consisting of an inorganic nitride, an organic tin compound, a compound that generates ammonia, and a crosslinking agent.
• the crosslinked product of the present disclosure can be suitably used as a sealing material.
• the crosslinked product of the present disclosure preferably has a compression set of 50% or less, which is measured by leaving it at 300° C. for 70 hours at a compression rate of 25%.
• composition of the present disclosure contains a perfluoroelastomer and a filler.
• Patent Document 1 discloses that non-oxide ceramics such as carbides and nitrides are used as fillers in cross-linkable elastomer compositions to prevent NF 3 plasma treatment and O 3 treatment exposed in the semiconductor manufacturing process. It is stated that molded products with small weight changes can be obtained in both cases. Further, Patent Document 2 discloses that by using silicon carbide particles having a bulk density of 0.15 g/cm 3 or less as a filler to be blended into a crosslinkable fluorine-containing elastomer composition, O 2 plasma treatment and O 2 /CF 4 It is stated that molded products with small weight changes can be obtained by plasma treatment.
• the filler contains silicon carbide and graphite, and the area of the peak derived from silicon carbide in the filler (SiC) measured by X-ray photoelectron spectroscopy (XPS)
• XPS X-ray photoelectron spectroscopy
• the filler contained in the composition of the present disclosure contains silicon carbide and graphite, and has a ratio (area (C)/area (SiC)) of 0.7 or more.
• the area of the peak derived from silicon carbide in the filler (SiC) and the area of the peak derived from graphite in the filler (C) can be determined by analyzing the filler using X-ray photoelectron spectroscopy.
• the peak area (SiC) and the peak area (C) are the areas of the peaks of carbon 1s derived from silicon carbide and graphite in the filler.
• the ratio of the filler (area (C)/area (SiC)) is preferably 1.0 or more, more preferably 1.6, since this further improves the plasma resistance and compression set resistance of the crosslinked product. or more, preferably 3.0 or less, more preferably 2.0 or less.
• the filler of the present disclosure contains silicon carbide and graphite.
• the fact that the filler contains silicon carbide and graphite can be confirmed by, for example, using a transmission electron microscope (TEM) equipped with an energy dispersive X-ray spectrometry (EDS) device to obtain a transmission electron micrograph of the filler and an elemental mapping image of carbon element. You can check this by getting it.
• TEM transmission electron microscope
• EDS energy dispersive X-ray spectrometry
• the content of graphite is preferably 0 to 10% by mass, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably The content is 1.0% by mass or more, more preferably 8.0% by mass or less, even more preferably 6.0% by mass or less, particularly preferably 5.0% by mass or less.
• the filler contained in the composition of the present disclosure also includes a filler containing such a trace amount of graphite that weight loss cannot be measured by simultaneous differential thermogravimetric measurement.
• the content of graphite can be measured by the following method. That is, using a simultaneous differential thermogravimetric measurement device, about 10 mg of filler was heated in an air atmosphere, and the temperature of the filler was raised from room temperature to 1000 °C at a rate of 10 °C/min, and the weight decreased the most. Measure the weight at the time. Next, by subtracting the weight at the time when the weight decreases the most from the initial weight (weight at room temperature before heating), the amount of weight loss at the time the weight decreases the most is calculated. Then, as the weight reduction rate, the ratio (%) of the weight reduction amount at the time when the weight decreases the most to the initial weight is calculated.
• normal temperature may be a temperature in the range of 10 to 40°C. The temperature range of 10 to 40° C. does not significantly affect the calculated weight loss percentage.
• the filler contains silicon carbide and graphite
• the content of graphite in the filler can be determined by determining the weight reduction rate of the filler.
• the BET specific surface area of the filler determined by the nitrogen adsorption method is preferably 15 to 150 m 2 /g, more preferably 20 m 2 since the plasma resistance and compression set resistance of the obtained crosslinked product are further improved. /g or more, more preferably 40 m 2 /g or more, even more preferably 50 m 2 /g or more, more preferably 100 m 2 /g or less, and still more preferably 80 m 2 /g or less. .
• the BET specific surface area of the filler determined by the nitrogen adsorption method can be measured by the BET flow method (one point method) using nitrogen gas and mixed gas (30% nitrogen + 70% helium).
• the BET specific surface area of the filler determined by the water vapor adsorption method is preferably 1 to 15 m 2 /g, more preferably 3 m 2 since this further improves the plasma resistance and compression set resistance of the crosslinked product obtained. /g, more preferably 4 m 2 /g or more, more preferably 12 m 2 /g or less, even more preferably 10 m 2 /g or less.
• the BET specific surface area of the filler determined by the water vapor adsorption method can be calculated by measuring the water vapor adsorption of the filler, obtaining a water vapor adsorption/desorption isotherm, and using the water vapor adsorption/desorption isotherm according to the BET method.
• the ratio of the BET specific surface area of the filler determined by the water vapor adsorption method to the BET specific surface area of the filler determined by the nitrogen adsorption method further improves the plasma resistance and compression set resistance of the obtained crosslinked product. Therefore, it is preferably 1 to 60%, more preferably 3 to 40%, even more preferably 4% or more, even more preferably 5% or more, and even more preferably 30% or less, More preferably, it is 20% or less.
• the ratio of the BET specific surface area of the filler determined by the water vapor adsorption method to the BET specific surface area of the filler determined by the nitrogen adsorption method is an index of the degree of hydrophilicity of the filler, and the higher the ratio (water vapor/nitrogen) This means that the filler has a high degree of hydrophilicity.
• the bulk density of the filler is preferably 0.10 g/cm 3 or more, more preferably 0.12 g/cm 3 or more, still more preferably 0.14 g/cm 3 or more, and more preferably 0.30 g /cm 3 or less, more preferably 0.20 g/cm 3 or less.
• the bulk density of the filler can be calculated from the volume by putting 5 g of powder into a 100 ml graduated cylinder (inner diameter 28 mm) and reading the scale after tapping 20 times from a height of 2 cm.
• the average particle diameter of the filler is preferably 10 to 100 nm, more preferably 15 nm or more, and even more preferably 20 nm or more, since this further improves the plasma resistance and compression set resistance of the resulting crosslinked product. , more preferably 90 nm or less, still more preferably 80 nm or less.
• the filler used in the present disclosure is preferably manufactured by a thermal plasma method.
• the filler used in the present disclosure may be, for example, silicon powder or silicon carbide powder introduced into a hot plasma flame using an inert gas as a carrier gas to be evaporated into a gas phase mixture, and carbonized with the gas phase mixture. It can be produced by contacting it with hydrogen gas.
• JP2007-138287A, JP2011-213524A, non-patent literature Ya-Li LI and Takamasa ISHIGAKI, “Synthesis and Structural Characterization of Core-Shell Si-SiC Composite Particles by Thermal Plasma In- Flight Carburization of Silicon Powder”, Journal of the Ceramic Society of Japan, 2007, 115(11), p.717-723). SiC)
• SiC SiC
• the content of the filler in the composition of the present disclosure is preferably from 0.1 to 100 parts by mass based on 100 parts by mass of the perfluoroelastomer, since the resulting crosslinked product further improves the plasma resistance and compression set resistance.
• 100 parts by mass more preferably 0.5 parts by mass or more, still more preferably 1.0 parts by mass or more, particularly preferably 5 parts by mass or more, more preferably 50 parts by mass or less, More preferably, it is 30 parts by mass or less, particularly preferably 25 parts by mass or less.
• the composition of the present disclosure further improves the plasma resistance and compression set resistance of the crosslinked product, so it has a sea-island structure formed from islands made of filler and seas made of perfluoroelastomer. It is preferable to have.
• a sea-island structure can be formed by blending a filler containing silicon carbide and exhibiting the above ratio (area (C)/area (SiC)) into a perfluoroelastomer.
• silicon carbide is formed by highly dispersed silicon carbide in the perfluoroelastomer, especially when the BET specific surface area (nitrogen adsorption method) or average particle size of silicon carbide is small.
• a composition having a network structure is obtained.
• a filler exhibiting the above ratio (area (C)/area (SiC)) is used, even if the BET specific surface area (nitrogen adsorption method) or average particle diameter of the filler is small, a composition with a sea-island structure can be used. can get things.
• the state of dispersion of the filler in the composition can be confirmed, for example, by observing the surface or cut surface of the composition using a transmission electron microscope (TEM).
• TEM transmission electron microscope
• compositions of the present disclosure contain perfluoroelastomers.
• a perfluoroelastomer is a fluoropolymer in which the content of perfluoromonomer units based on the total polymerized units is 90 mol% or more, preferably 91 mol% or more, and has a glass transition temperature of 20°C or less.
• a fluoropolymer having a melting peak ( ⁇ H) size of 4.5 J/g or less and further, the concentration of fluorine atoms contained in the fluoropolymer is 71% by mass or more, preferably 71.5% by mass or more. It is a polymer.
• the concentration of fluorine atoms contained in the fluoropolymer is determined by calculating the concentration (% by mass) of fluorine atoms contained in the fluoropolymer from the type and content of each monomer constituting the fluoropolymer.
• a perfluoromonomer is a monomer that does not contain a carbon atom-hydrogen bond in its molecule.
• the perfluoromonomer may also be a monomer in which some of the fluorine atoms bonded to carbon atoms are replaced with chlorine atoms, and in addition to carbon atoms, nitrogen atoms and oxygen atoms. , a sulfur atom, a phosphorus atom, a boron atom, or a silicon atom.
• the perfluoromonomer is preferably a monomer in which all hydrogen atoms are replaced with fluorine atoms.
• the above perfluoromonomer does not include a monomer that provides a crosslinking site.
• the monomer that provides a crosslinking site is a monomer (cure site monomer) that has a crosslinking group that provides a fluoropolymer with a crosslinking site for forming crosslinks with a curing agent.
• each monomer constituting the perfluoroelastomer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, fluorescent X-ray analysis, and other known methods depending on the type of monomer.
• CF 2 CFO(CF 2 CF(Y 15 )O) m (CF 2 ) n F
• Y 15 represents a fluorine atom or a trifluoromethyl group.
• m is an integer of 1 to 4.
• n is an integer of 1 to 4.
• At least one type is preferred.
• Perfluoroelastomers include perfluoroelastomers containing TFE units, such as TFE/fluoromonomer copolymers represented by general formula (13), (14) or (15), and TFE/general formula (13), At least one selected from the group consisting of a fluoromonomer represented by (14) or (15)/a monomer copolymer that provides a crosslinking site is preferable.
• the composition is preferably 45-90/10-55 (mol%), more preferably 55-80/20-45. , more preferably 55-70/30-45, most preferably 56-69.5/30.5-44.
• the ratio is preferably 45 to 89.9/10 to 54.9/0.01 to 4 (mol%), more preferably 55 to 77.9/ 20-49.9/0.1-3.5, more preferably 55-69.8/30-44.8/0.2-3, most preferably 55.3-69.5/30. It is 3-44.5/0.2-2.8.
• the ratio is preferably 50 to 90/10 to 50 (mol%), More preferably 60-88/12-40, still more preferably 65-85/15-35, most preferably 66-84/16-34.
• TFE/fluoromonomer represented by general formula (13), (14) or (15) having 4 to 12 carbon atoms/monomer copolymer providing a crosslinking site preferably 50 to 89.9/10 to 49.9/0.01 to 4 (mol%), more preferably 60 to 87.9/12 to 39.9/0.1 to 3.5, even more preferably 65 to 84.8/ 15-34.8/0.2-3, most preferably 66-84.3/15.5-33.8/0.2-2.8.
• the composition falls outside of these ranges, the properties as a rubber elastic body tend to be lost and the properties become close to those of a resin.
• perfluoroelastomers examples include TFE/fluoromonomer represented by general formula (15)/monomer copolymer providing a crosslinking site, TFE/fluoromonomer copolymer represented by general formula (15), TFE/general formula At least one selected from the group consisting of a fluoromonomer copolymer represented by (13), and TFE/fluoromonomer represented by general formula (13)/a monomer copolymer that provides a crosslinking site. is preferred.
• perfluoroelastomers examples include perfluoroelastomers 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. I can do it.
• the monomer that provides a crosslinking site is a monomer (cure site monomer) that has a crosslinking group that provides the perfluoroelastomer with a crosslinking site for forming a crosslink with a crosslinking agent.
• CX 4 2 CX 5 R f 2 X 6
• X 4 and X 5 are each independently H, F, or an alkyl group having 1 to 5 carbon atoms, and R f 2 may have one or more ether-bonding oxygen atoms.
• a linear or branched alkylene group or oxyalkylene group which may have an aromatic ring and in which some or all of the hydrogen atoms may be substituted with fluorine atoms
• X 6 is an iodine atom , a bromine atom, a nitrile group, a carboxyl group, an alkoxycarbonyl group, a hydroxyl group, a vinyl group, an azide group, a sulfonyl azide group, a carbonyl azide group, or an alkyne group.
• the alkyne group may be an ethynyl group.
• CX 16 2 CX 16 -Rf 16 CHR 16 X 17
• X 16 is each independently a hydrogen atom, a fluorine atom, or CH 3
• Rf 16 is a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group, or a perfluoro(poly)oxyalkylene group.
• Z is a linear or branched alkyl group having 1 to 18 carbon atoms, which may have an oxygen atom.
• Q is an alkylene group or an oxyalkylene group.
• p is 0 or 1.
• m/n is 0.2 to 5.
• ) is preferably at least one selected from the group consisting of monomers represented by the following.
• X 16 is a fluorine atom.
• Rf 16 and Rf 17 are preferably perfluoroalkylene groups having 1 to 5 carbon atoms.
• R 16 is preferably a hydrogen atom.
• X 18 is preferably a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH 2 I.
• X 19 is preferably a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH 2 OH.
• the perfluoroelastomer preferably has a glass transition temperature of -30°C or higher, more preferably -20°C or higher, and even more preferably -10°C or higher, since it has excellent compression set characteristics at high temperatures. preferable. Further, from the viewpoint of good cold resistance, the temperature is preferably 10°C or lower, more preferably 5°C or lower, and even more preferably 0°C or lower.
• the above glass transition temperature was determined by obtaining a DSC curve by heating 10 mg of a sample at a rate of 10°C/min using a differential scanning calorimeter (manufactured by Mettler Toledo, DSC822e). It can be determined as the temperature indicating the midpoint of the two intersections of the extension of the line and the tangent at the inflection point of the DSC curve.
• the perfluoroelastomer preferably has a Mooney viscosity ML (1+20) at 170° C. of 30 or more, more preferably 40 or more, and even more preferably 50 or more. In addition, from the viewpoint of good workability, it is preferably 100 or less, more preferably 90 or less, and even more preferably 80 or less.
• the perfluoroelastomer preferably has a Mooney viscosity ML (1+20) at 140°C of 30 or more, more preferably 40 or more, and even more preferably 50 or more. In addition, from the viewpoint of good workability, it is preferably 180 or less, more preferably 150 or less, and even more preferably 110 or less.
• the perfluoroelastomer preferably has a Mooney viscosity ML (1+10) at 100° C. of 10 or more, more preferably 20 or more, and even more preferably 30 or more. In addition, from the viewpoint of good workability, it is preferably 120 or less, more preferably 100 or less, and even more preferably 80 or less.
• the above Mooney viscosity can be measured according to JIS K6300 at 170°C, 140°C, or 100°C using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES.
• Perfluoroelastomers can be produced by conventional methods, but the molecular weight distribution of the resulting polymer is narrow, the molecular weight can be easily controlled, and iodine atoms or bromine atoms can be introduced at the terminals. It is also possible to use iodine or bromine compounds as chain transfer agents. Examples of the polymerization method using an iodine compound or a bromine compound include a method of carrying out emulsion polymerization in an aqueous medium under pressure in the presence of an iodine compound or a bromine compound in a substantially anoxic state. (Iodine transfer polymerization method).
• iodine compound or bromine compound to be used include, for example, the general formula: R 21 I x Bry (In the formula, x and y are each an integer of 0 to 2 and satisfy 1 ⁇ x+y ⁇ 2, and R 21 is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or a chlorofluorocarbon group. Examples include compounds represented by a hydrocarbon group or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom.
• iodine or bromine compounds iodine or bromine atoms are introduced into the polymer and serve as crosslinking points.
• iodine compounds and bromine compounds include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1 , 5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodo Perfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, CF 2 Br 2 , BrCF 2 CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2 , BrCF 2
• 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are preferred from the viewpoint of polymerization reactivity, crosslinking reactivity, easy availability, etc. is preferred.
• the perfluoroelastomer preferably has a cyano group (-CN group).
• Perfluoroelastomers having a cyano group (-CN group) are those in which the cyano group can be crosslinked by cyclization trimerization to form a triazine ring, or those in which the cyano group can be crosslinked by forming a triazine ring using a tetramine compound as a crosslinking agent. It can be cross-linked by the process, and can impart excellent compression set properties and heat resistance to the cross-linked product.
• the above-mentioned perfluoroelastomer having a cyano group preferably has a cyano group (-CN group) at the end of the main chain and/or at the side chain.
• the content of monomer units having a cyano group (-CN group) is determined by combining TFE units with general formulas (13), (14) and (15). The amount may be 0.1 to 5 mol%, and may be 0.3 to 3 mol%, based on the total amount with the fluoromonomer units. Further preferred compositions are as described above.
• CY 1 2 CY 1 (CF 2 ) n -CN
• Y 1 is each independently a hydrogen atom or a fluorine atom, and n is an integer from 1 to 8)
• Formula: CF 2 CFCF 2 Rf 8 -CN (In the formula, Rf 8 is -(OCF 2 ) n - or -(OCF(CF 3 )) n -, where n is an integer from 0 to 5)
• Formula: CF 2 CFCF 2 (OCF(CF 3 )CF 2 ) m (OCH 2 CF 2 CF 2 ) n OCH 2 CF 2 -CN (In the formula, m is an integer from 0 to 5, and n is an integer from 0 to 5.)
• Formula: CF 2 CFCF 2 (OCH 2 CF 2 CF 2 ) m (OCF(CF 3 )CF 2 ) n OCF(
• perfluoroelastomers include fluororubbers 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. can be given.
• composition of the present disclosure may further contain a filler other than the silicon carbide described above.
• fillers include imide fillers with an imide structure such as polyimide, polyamideimide, and polyetherimide, and engineering plastics such as polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyetherketone, and polyoxybenzoate.
• organic fillers such as silicon oxide, aluminum oxide, yttrium oxide, metal carbides such as aluminum carbide, metal nitride fillers such as silicon nitride, aluminum nitride, carbon black, aluminum fluoride, carbon fluoride, etc. Examples include inorganic fillers.
• carbon black aluminum oxide, silicon oxide, yttrium oxide, silicon nitride, polyimide, and carbon fluoride are preferred from the viewpoint of shielding effects against various plasmas.
• inorganic fillers and organic fillers may be used alone or in combination of two or more.
• additives such as processing aids, plasticizers, colorants, etc.
• processing aids plasticizers, colorants, etc.
• One or more types of commonly used crosslinking agents and crosslinking aids different from the above may be blended.
• the above composition may contain an organic basic compound.
• DBU 1,8-diazabicycloundec-7-ene
• composition of the present disclosure may further contain at least one selected from the group consisting of inorganic nitrides, organic tin compounds, compounds that generate ammonia, and crosslinking agents.
• a crosslinking agent such as a crosslinking agent, a crosslinked product can be easily obtained from the composition of the present disclosure.
• inorganic nitrides include, but are not limited to, silicon nitride (Si 3 N 4 ), lithium nitride, titanium nitride, aluminum nitride, boron nitride, vanadium nitride, zirconium nitride, and the like.
• silicon nitride is preferred because nano-sized particles can be supplied.
• organic tin compounds examples include tetraphenyltin and triphenyltin.
• the compound that generates ammonia is preferably a compound that generates ammonia at a temperature of 40 to 330°C.
• ammonia-generating compound urea or a derivative thereof, or an ammonium salt is preferable, urea or an ammonium salt is more preferable, and urea is even more preferable.
• the ammonium salt may be an organic ammonium salt or an inorganic ammonium salt. Further, the ammonia-generating compound may be one that reacts with a trace amount of water to generate ammonia.
• urea derivatives examples include biurea, thiourea, urea hydrochloride, and biuret.
• organic ammonium salts include ammonium salts of non-fluorine carboxylic acids or sulfonic acids such as ammonium benzoate, ammonium adipate, and ammonium phthalate.
• inorganic ammonium salts include compounds described in JP-A-9-111081, such as ammonium sulfate, ammonium carbonate, ammonium nitrate, and ammonium phosphate.
• ammonia-generating compounds examples include acetaldehyde ammonia, hexamethylenetetramine, formamidine, formamidine hydrochloride, formamidine acetate, t-butyl carbamate, benzyl carbamate, and phthalamide.
• crosslinking agent examples include those used in peroxide crosslinking, polyol crosslinking, polyamine crosslinking, triazine crosslinking, oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking.
• the perfluoroelastomer has a cyano group (-CN group)
• the crosslinking agent is preferably at least one selected from the group consisting of oxazole crosslinking agents, imidazole crosslinking agents, and thiazole crosslinking agents.
• the crosslinking agent used in peroxide crosslinking may be any organic peroxide that can easily generate peroxy radicals in the presence of heat or a redox system.
• dialkyl type ones are preferred.
• 2,5-dimethyl-2,5-di(t-butylperoxy)hexane is particularly preferred.
• the type and amount of organic peroxide to be used are selected in consideration of the amount of active -O-O-, decomposition temperature, etc.
• triallyl cyanurate triallyl isocyanurate (TAIC), triallyl formal, triallyl trimellitate, N,N'-n-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl Terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallylisocyanurate (1,3,5-tris(2,3,3-trifluoro-2-propenyl)-1,3,5-triazine 2,4, 6-trione), tris(diallylamine)-S-triazine, triallyl phosphite, N,N-diallylacrylamide, and 1,6-divinyldodecafluorohexane.
• TAIC triallyl cyanurate
• triallyl formal triallyl trimellitate
• N,N'-n-phenylene bismaleimide dipropargyl terephthalate
• diallyl phthalate
• crosslinking aid used together with a peroxide crosslinking agent general formula (31):
• the six R 31s are each independently H, a halogen atom, or an optionally halogenated group having 1 to 5 carbon atoms, into which an ether bond may be inserted.
• Z 31 is a linear or branched optionally halogenated alkylene group having 1 to 18 carbon atoms, a cycloalkylene group, or a (per)fluoropolyoxy group, which optionally contains a heteroatom.
• Compounds represented by alkylene groups can also be mentioned.
• general formula (32) (In the formula, j is an integer of 2 to 10, preferably 4 to 8, and each of the four R 32s is independently H, F, an alkyl group having 1 to 5 carbon atoms, or a (per)fluoro is an alkyl group), a compound represented by general formula (33): (wherein, Y 31 is each independently F, Cl , or H, and Y 32 is each independently F, Cl, H, or OR 33 (branched or straight-chain alkyl group, which may be substantially or completely fluorinated or chlorinated), and Z 33 is an optionally fluorinated alkyl group, which may have an ether bond inserted.
• R 35 to R 37 are each independently a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, or a substituted or unsubstituted aryl group, and at least one of R 35 to R 37 is a fluorine atom or a group containing a fluorine atom.
• m is an integer of 1 to 5. When m is 2 or more, m R 35 to R 37 may be the same or different. (The hydrogen atom of the benzene ring may be substituted.)
• Compounds having at least one structure represented by the following can also be mentioned. When m is 1, it is preferable to have two or more of the structures.
• R 35 to R 37 are as described above.
• R 38 is a single bond, -SO 2 -, -O-, -S-, -CO-, a heteroatom-containing group, a substituted or unsubstituted An alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group.
• m is an integer from 1 to 5. These groups may be partially or completely fluorinated.
• Examples include compounds represented by:
• the heteroatom-containing group is not particularly limited as long as it is a divalent group containing a heteroatom.
• heteroatoms include oxygen atom, nitrogen atom, sulfur atom, boron atom, and phosphorus atom.
• crosslinking agents used for polyol crosslinking include polyhydric alcohol compounds such as bisphenol A and bisphenol AF.
• crosslinking agent used for polyamine crosslinking examples include polyvalent amine compounds such as hexamethylene diamine carbamate, N,N'-dicinnamylidene-1,6-hexanediamine, and 4,4'-bis(aminocyclohexyl)methane carbamate.
• crosslinking agents used for oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking include general formula (41):
• R 41 is -SO 2 -, -O-, -CO-, an alkylene group having 1 to 6 carbon atoms, a perfluoroalkylene group having 1 to 10 carbon atoms, or a single bond, or
• R 42 and R 43 is -NH 2 and the other is -NHR 44 , -NH 2 , -OH or -SH, and R 44 is a hydrogen atom, a fluorine atom or a monovalent They are organic groups, preferably R 42 is -NH 2 and R 43 is -NHR 44 .
• R 42 is -NH 2 and R 43 is -NHR 44 .
• Preferred specific examples of the alkylene group having 1 to 6 carbon atoms include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, etc.
• R 41 is as described above, and R 45 is each independently any of the following groups.
• Rf 41 is a perfluoroalkylene group having 1 to 10 carbon atoms
• n is an integer of 1 to 10
• R 49 is Ph, COOC(CH 3 ) 3 , NH 2 , CH 2 COOH, CSNH 2 , CNHNH 3 + Cl ⁇ , p-phenylCN, and COPh).
• bisaminophenol crosslinking agents, bisaminothiophenol crosslinking agents, bisdiaminophenyl crosslinking agents, etc. are conventionally used in crosslinking systems with cyano groups as crosslinking points, but they also contain carboxyl groups and alkoxycarbonyl groups. It also reacts with groups to form oxazole rings, thiazole rings, and imidazole rings, giving crosslinked products.
• X 41 -( CH 2 ) n -R 50 -(CH 2 ) m -X 41 (wherein, or Y 41 P N 3 (Y 41 is SO, SO 2 , C 6 H 4 or CO, p is 0 or 1), and n and m are independently integers from 1 to 4;
• R 50 is i) a fluoroalkylene group having 3 to 10 carbon atoms, ii) a fluoroalkoxylene group having 3 to 10 carbon atoms, iii) substituted arylene group, iv) an oligomer containing copolymerized units of vinylidene fluoride and perfluoro(methyl vinyl ether); v) an oligomer containing copolymerized units of vinylidene fluoride and hexafluoropropylene; vi) an oligomer comprising copolymerized units of tetrafluoroethylene and
• This crosslinking agent is preferably used with a perfluoroelastomer having a nitrile group, an azide group, a sulfonyl azide group, a carbonyl azide group or an alkyne group.
• a perfluoroelastomer having a nitrile group, an azide group, a sulfonyl azide group, a carbonyl azide group or an alkyne group.
• the nitrile group of the perfluoroelastomer and the azide group of the crosslinking agent react to form a tetrazole ring and give a crosslinked product.
• crosslinking agents include compounds having multiple 3-amino-4-hydroxyphenyl groups or 3-amino-4-mercaptophenyl groups, or compounds having the general formula (47):
• R 41 , R 42 and R 43 are as described above.
• Specific examples include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.
• 2,2-bis[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane is preferred as a crosslinking agent because of its heat resistance, steam resistance, amine resistance, and good crosslinking properties. is preferred.
• the content of at least one selected from the group consisting of inorganic nitrides, organic tin compounds, compounds that generate ammonia, and crosslinking agents is preferably 0.05 to 10 parts by mass based on 100 parts by mass of the perfluoroelastomer.
• the amount is more preferably 0.1 to 5.0 parts by weight, still more preferably 0.2 to 2.0 parts by weight, and particularly preferably 0.3 to 1.0 parts by weight.
• the above composition can be prepared by mixing the above components using a conventional polymer processing machine, such as an open roll, a Banbury mixer, or a kneader. In addition, it can also be prepared by a method using an internal mixer.
• the above composition can be suitably used as a molding material for obtaining a crosslinked product by crosslinking molding.
• a crosslinked product can be obtained by crosslinking the composition of the present disclosure.
• the crosslinked product of the present disclosure has excellent durability against both O 2 plasma and CF 4 plasma, and has low compression set even when used at high temperatures exceeding 300°C.
• the crosslinked product of the present disclosure has a compression set of preferably 50% or less, more preferably 46% or less, as measured by standing at 300° C. for 70 hours at a compression ratio of 25%.
• Compression set is determined by compressing the crosslinked product at a compression rate of 25% and leaving it at 300°C for 70 hours, then leaving it at 70°C for 24 hours, then releasing the compression and leaving it at 20°C for 30 minutes. After that, it can be calculated by measuring the thickness of the crosslinked product before and after compression.
• Examples of the method for obtaining a crosslinked product from the composition include a method in which a preform is obtained by molding the composition as a molding material, and then the preform is crosslinked.
• a preform can be obtained from the above composition by any conventional method, such as heating compression using a mold, press-fitting into a heated mold, extrusion using an extruder, or other known methods. can.
• crosslinked products can be obtained by heat crosslinking using steam or the like after extrusion.
• the above crosslinking can be performed in the order of primary crosslinking and secondary crosslinking.
• the primary crosslinking is preferably carried out at 150 to 250°C for 5 to 120 minutes, more preferably at 170 to 200°C for 5 to 60 minutes.
• any known crosslinking means may be used, such as press crosslinking.
• the secondary crosslinking is preferably carried out at 200 to 320°C for 2 to 48 hours, more preferably at 250 to 310°C for 5 to 24 hours. Further, the temperature may be varied within this temperature range.
• any known crosslinking means may be used, such as oven crosslinking.
• the crosslinking atmosphere may be an air atmosphere or an inert atmosphere such as nitrogen.
• the crosslinked product of the present disclosure can be suitably used as a sealing material for semiconductor manufacturing equipment that particularly requires heat resistance, especially semiconductor manufacturing equipment that performs high-density plasma irradiation.
• the sealing material include O-rings, square rings, gaskets, packings, oil seals, bearing seals, lip seals, and the like.
• it can be used as various polymer products used in semiconductor manufacturing equipment, such as diaphragms, tubes, hoses, various rubber rolls, and belts. It can also be used as a coating material or lining material.
• the semiconductor manufacturing equipment referred to in this disclosure is not limited to equipment specifically for manufacturing semiconductors, but broadly refers to semiconductors that require a high level of cleanliness, such as equipment for manufacturing liquid crystal panels and plasma panels. It includes all manufacturing equipment used in the field, and examples include the following.
• the crosslinked product of the present disclosure exhibits excellent performance as a sealing material for, for example, a CVD device, a plasma etching device, a reactive ion etching device, an ashing device, or an excimer laser exposure machine.
• BET specific surface area of filler nitrogen adsorption method, water vapor adsorption method
• the BET specific surface area of the filler determined by the nitrogen adsorption method is determined by the BET flow method using nitrogen gas and mixed gas (30% nitrogen + 70% helium) using a fully automatic BET specific surface area measuring device Macsorb HM-1208 manufactured by Mountech. (1 point method).
• the BET specific surface area of the filler determined by the water vapor adsorption method was determined by vacuum degassing the filler at 100°C for 3 hours, and using a high-precision gas/vapor adsorption measurement device BELLSORP-maxII manufactured by Microtrac Bell Co., Ltd., at 25°C.
• the adsorption isotherm was obtained by analyzing this isotherm using the BET method.
• the graphite content was determined by heating the filler in air to 1000°C at 10°C/min using a simultaneous differential thermogravimetry analyzer STA7200 manufactured by Hitachi High-Tech Science. It is a value.
• the peak positions were set to 283.5 ⁇ 0.5 eV, 284.8 ⁇ 0.6 eV, 286.0 ⁇ 0.5 eV, and 289.1 ⁇ 0.5 eV in descending order of binding energy.
• the peak at 283.5 ⁇ 0.5 eV was defined as a peak derived from SiC
• the peak at 284.8 ⁇ 0.6 eV was defined as a peak derived from graphite. Based on the results of the peak separation process, the ratio of the area of the peak attributable to graphite to the area of the peak attributable to SiC (peak area of graphite/peak area of SiC) was calculated.
• compression set Compression set was measured according to the method described in ASTM D395 or JIS K6262.
• the O-rings produced in 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). did.
• the compression device to which the compressed O-ring was fixed was placed in an electric furnace, left at 300° C. for 70 hours or 168 hours, and then taken out from the electric furnace. Thereafter, the compression device to which the compressed O-ring was fixed was placed in another electric furnace and left at 70° C. for 24 hours.
• the O-rings (P24 size) produced in Examples and Comparative Examples were placed in a process chamber. Plasma generated using a radical generator was sent into a process chamber, and the O-ring was irradiated with the plasma under the following plasma irradiation conditions. The ICP plasma weight reduction rate of O 2 and CF 4 was calculated from the mass of the O ring before and after plasma irradiation.
• Radical generator ICP high-density plasma device (RIE-101iPH manufactured by SAMCO) Gas flow rate: 16sccm Power: 400W Pressure: 2.66Pa Irradiation time: 1 hour
• the O-ring (P24 size) was irradiated with plasma.
• the mass of the O-ring after plasma irradiation was measured, and then the particles present on the surface were removed by wiping the O-ring after plasma irradiation with a nonwoven cloth impregnated with ethanol, and then heated in an oven at 150 ° C. After drying for 1 hour, the mass of the O-ring was measured again.
• the difference in mass before and after wiping corresponds to the mass of surface particles.
• the ratio of the mass of surface particles to the mass before wiping (the amount of particles generated) was calculated.
• Crosslinking agent 2,2-bis[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane
• Filler Fillers 1 to 4 Graphite coating silicon carbide Filler 5: Silicon carbide Filler 6: Silicon carbide (DU A-1 manufactured by Showa Denko)
• Table 1 shows the physical properties of each filler.
• the obtained composition was crosslinked by pressing at 180°C for 30 minutes, and then oven crosslinked in an air oven at 290°C for 18 hours to produce a P24 size O-ring.
• compression set, ICP plasma weight reduction rate, and particle generation amount were measured by the methods described above. The results are shown in Table 2.

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