Fluorine-containing elastomer composition containing microdiamonds

Abstract

The curable fluorine-containing elastomer compositions herein comprise at least one curable fluoropolymer having at least one fluorine-containing cure site monomer, including at least one fluorinated monomer and at least one cure site, at least one curing agent, and microdiamond particles having an average particle size of greater than 0.1 microns to about 100 microns. Such compositions may be fluorinated or perfluorinated. Articles formed from the compositions herein can be used at high service temperatures and exhibit one or more of reduced particulates, reduced high-temperature compression set values, reduced adhesion, improved resistance to fluorine-based plasma, oxygen-based plasma, hydrogen-based plasma, and combinations thereof, and improved physical properties.

Description

[Technical Field]

[0001] Cross-references to related applications This U.S. non-provisional patent application asserts, under § 119(e) the interests of U.S. Provisional Patent Application No. 62 / 891,865, titled “Fluorine-Containing Compositions Including Microdiamond,” filed on 26 August 2019, the full disclosure of which is incorporated herein by reference.

[0002] Background of the Invention Field of Invention The present invention relates to a fluoroelastomer composition incorporating a microdiamond filler to provide one or more of the following properties: reduced particle size, reduced high-temperature compression set, reduced adhesion, improved plasma resistance in fluorine-based plasmas, oxygen-based plasmas, hydrogen-based plasmas and mixtures of such plasmas, ability to operate at high operating temperatures, and improved physical properties. [Background technology]

[0003] Description of related technologies Fluorine-containing elastomers, including fluoroelastomers (FKMs), perfluoroelastomers (FFKMs), and blends thereof, containing tetrafluoroethylene (TFE) and other partially or fully fluorinated monomers, are well-known for their chemical resistance, solvent resistance, and thermal resistance, and are therefore widely used for sealing materials and other materials used in harsh environments. The required characteristics of such materials are highly specific to these end applications, and the demand for highly resistant compounds, particularly FFKM compounds used in semiconductors and other "clean" processes where contamination must be avoided, continues to grow. In the fields of aeronautics, aerospace, semiconductors, and the manufacture of chemicals and pharmaceuticals, sealing properties are exposed to harsh chemical environments, which can reach extremely high temperatures of over 350°C, and the ability of such materials to withstand such high-temperature environments and / or harsh chemicals, such as oxygen-based plasmas, fluorine-based plasmas, and / or hydrogen-based plasmas, is becoming increasingly important. Therefore, in this art, there is a need to develop elastomers that reduce particulate matter formation from seals, especially at higher operating temperatures, reduce compression set, improve plasma resistance, reduce adhesion, and improve physical properties. The development of elastomer encapsulation compositions that can achieve such capabilities and operate in such harsh environments remains a continuing need in this art.

[0004] The goal is to form molded parts, such as seals and gaskets, that can withstand deformation and endure such harsh conditions using such good, high-temperature and environmentally resistant materials. Strength and other physical properties benefit from the filler formulation, but the addition of additives can usually negatively affect compression set and other elastomer sealing properties, as well as plasma resistance and adhesion. Therefore, it is necessary to carefully select and balance the fillers used to achieve sufficient strength, low adhesion and the ability to withstand harsh plasma and high-temperature conditions, as well as to maintain sufficient sealing properties, such as a moderately low compression set.

[0005] FFKM materials are typically prepared from perfluoropolymers containing at least one perfluorocurable site monomer having a functional group with curable sites. The monomers polymerize to form a curable perfluoropolymer having curable sites, and this polymer is intended to be crosslinked by reaction with a curing agent. During curing (crosslinking), the material forms an elastomer. A typical FFKM composition includes a perfluoropolymer, a curing agent that reacts with the reactive curable site groups on the curable site monomer, and any desired filler. The resulting cured perfluoroelastomer material exhibits elastomer characteristics. FKM also generally contains one or more perfluoropolymers, but non-perfluoropolymers, such as vinylidene fluoride, can also be incorporated, and this vinylidene fluoride can act as both a monomer and a curable site.

[0006] FFKM and / or FKM are also commonly known for their use as O-rings and in related sealing components for high-end sealing applications. FFKM, in particular, has been explored for its use due to its high degree of thermal resistance, as well as its resistance to plasma, chemicals, and other harsh environments. To meet the growing demand and challenges, novel perfluoroelastomer compositions are continuously being developed to achieve even higher levels of thermal, chemical, and / or plasma resistance, and to develop physical properties suitable for various end applications, with ongoing attempts to reduce particulate matter and maintain or lower compression set, especially at high temperatures and with lower adhesion. Industry demand, particularly in the semiconductor sector, continues to require improved performance of such seals to meet the requirements of increasingly harsh environments for new end applications, as well as the increasingly low contamination and particulate matter requirements, while maintaining sufficient elastomer sealing, physical strength, and low adhesion. Therefore, there is always a need for better properties, specifically by using compounds with lower particulate matter, i.e., compounds that introduce little to no harmful contaminants into the end-use environment.

[0007] The fillers and filler combinations used to achieve the targeted properties and elastomeric properties in conventional technologies include both inorganic and organic fillers. Typical fillers known in the semiconductor and other industries include carbon black, silica, alumina, TFE-based fluoropolymers, barium sulfate, graphite fluoride, nanodiamonds, treated carbon, and other polymers and plastics. Fillers used in some FFKM compositions for semiconductor applications include various fluoropolymer filler particles formed from polytetrafluoroethylene (PTFE) or perfluoropolymers, such as copolymers of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) (also known as FEP-type copolymers) or copolymers of TFE and perfluoroalkyl vinyl ether (PAVE) (known as PFA-type copolymers).

[0008] Examples of such FFKM and / or FKM compositions include a single curable polymer or sometimes a blend of one or more such curable polymers. Similarly, there are fluorine-containing elastomers having a single curable site on the curable site monomer in the curable perfluoropolymer used in the composition, or having one or more curable site monomers having the same or different curable sites.

[0009] Many potential combinations of materials can be used, and the challenge is to achieve higher thermal resistance, chemical resistance, and plasma resistance properties for various end applications, without sacrificing mechanical properties and sealing properties, such as compression set, and preferably while improving such properties.

[0010] One attempt to introduce plasma-resistant properties can be found in U.S. Patent Application Publication 2009 / 0023852A1, which describes a fluorine-containing elastomer composition for use in preparing molded articles that exhibit small weight changes when exposed to NF3, O2, and CF4 plasmas. The composition comprises a fluorine-containing elastomer and a nano-sized carbon allotrope having an average particle size of at most 0.1 microns, which may be diamond. The publication teaches that particle sizes larger than 0.1 microns cause problems and affect the defect rate of semiconductors, and points out that if the individual particle sizes in the filler are larger than 0.1 microns, the filler should be further ground to smaller sizes.

[0011] U.S. Patent No. 6,946,513B2 provides an elastomer composition prepared using a pure filler suitable as a molding material for semiconductor manufacturing equipment. The filler may be a carbon filler, such as carbon black, graphitized carbon, or graphite. The filler may be in the form of particles or fibers, and the particle size is preferably 5 microns or less.

[0012] U.S. Patent No. 9,725,582B2 provides a fluororesin composition for molded articles having good tensile strength. The fluororesin composition contains a fluororesin and fluorinated nanodiamonds present in an amount of 0.001 to 5% by mass relative to the fluororesin. The fluorinated nanodiamonds are described as a powder having an average particle size of 0.001 to 1 micron.

[0013] International Patent Publication WO2016 / 104604A1 describes a fluorine-containing elastomer composition used to form molded articles having improved chemical resistance, solvent resistance, and thermal resistance. The sealing material also demonstrates improved plasma resistance and can be used in the working chambers of semiconductor manufacturing equipment. The composition comprises a fluorine-containing elastomer having 0.0001 to 4 parts by mass of fullerene per 100 parts by mass of the fluorine-containing elastomer.

[0014] U.S. Patent No. 9,512,302B2 provides a fluoropolymer coating having improved tribological properties. In one embodiment, the present invention relates to a slurry composition of a fluoropolymer and nanodiamond particles having specific properties. The nanodiamond particles may be in single or aggregated form, and the particle size is preferably between 0.008 microns and 0.030 microns. The concentration of nanodiamonds in the slurry is at most 5% by weight.

[0015] As described above, in conventional technology, attempts have been made to integrate highly plasma-resistant carbon-based fillers into fluoroelastomers and perfluoroelastomers, for example, materials lacking resin strength. However, the use of high-strength particles, such as nanodiamonds, is taught to be undesirable if the particle size increases due to the defect rate (which is usually related to micronization or other factors, and it is not conceivable that strength can be obtained without loss of good elastomer properties in such materials). Therefore, there remains a need in the art to achieve or improve such sufficient physical properties while maintaining elastomer sealing properties and improving resistance to harsh plasma environments. [Prior art documents] [Patent Documents]

[0016] [Patent Document 1] U.S. Patent Application Publication No. 2009 / 0023852 [Patent Document 2] U.S. Patent No. 6,946,513 [Patent Document 3] U.S. Patent No. 9,725,582 [Patent Document 4] International Publication No. 2016 / 104604 [Patent Document 5] U.S. Patent No. 9,512,302 [Overview of the project] [Means for solving the problem]

[0017] Summary of the Invention The present invention, as described herein, includes a curable fluorine-containing elastomer composition comprising at least one curable fluoropolymer comprising at least one fluorinated monomer and at least one fluorine-containing curable site monomer comprising at least one curable site, and microdiamond particles having an average particle size of more than 0.10 microns to about 100 microns.

[0018] In one embodiment, the microdiamond particles may have an average particle size of greater than 0.1 microns to about 10 microns, or greater than about 0.1 microns to about 5 microns. The average particle size of the microdiamonds may also be about 0.20 microns to about 2 microns, or about 0.25 microns to about 1 micron. In a further embodiment, the microdiamond particles may have an average particle size of about 0.25 microns to about 0.5 microns. The microdiamond particles may have a shape selected from spherical particles, fibers, or flasks. The microdiamond particles may be natural and / or synthetic microdiamond particles. The particles may exist in the form of agglomerated or aggregated forms.

[0019] In one embodiment, the composition contains about 0.1 to about 100 parts by weight of microdiamond particles per 100 parts by weight of at least one curable fluoropolymer, preferably about 1 to about 50 parts by weight of microdiamond particles per 100 parts by weight of at least one curable fluoropolymer. More preferably, the composition contains about 2 to about 20 parts by weight of at least one curable fluoropolymer per 100 parts by weight.

[0020] At least one curable fluoropolymer may be a curable perfluoropolymer, at least one fluorinated monomer is tetrafluoroethylene, the perfluoropolymer may further contain a perfluoroalkyl vinyl ether monomer, and at least one fluorine-containing curable site monomer may be a perfluorinated curable site monomer.

[0021] In another embodiment, at least one curable fluoropolymer may be a curable perfluoropolymer, at least one fluorinated monomer may be tetrafluoroethylene, the curable perfluoropolymer may further contain a perfluoroalkyl vinyl ether monomer, and the curable perfluoropolymer may contain fluororesin particles therein.

[0022] In each of the embodiments of the compositions described above, the composition may also contain at least one curing agent that can be incorporated into the fluorine-containing elastomer composition before curing the composition. In one embodiment, the at least one curing agent may be a peroxide curing system.

[0023] The curable fluoropolymer may also be a first perfluoropolymer, wherein at least one fluorinated monomer is tetrafluoroethylene, and the perfluoropolymer further comprises a perfluoroalkyl vinyl ether monomer, each having at least one curable site, and there are at least two fluorine-containing curable site monomers, and the composition comprises two or more curing agents, one of which may be a peroxide curing system. In such embodiments, the curable fluorine-containing elastomer composition may comprise a blend of such a curable perfluoropolymer and a second curable perfluoropolymer comprising tetrafluoroethylene, a second perfluoroalkyl vinyl ether monomer and a perfluorinated curable site monomer, the second perfluoropolymer containing fluororesin particles therein, and may also comprise at least two curing agents, one of which may be a peroxide curing system.

[0024] In such blended fluoropolymer embodiments, the weight percentage ratio of the first curable perfluoropolymer to the weight of the second curable perfluoropolymer may range from about 5:95 to about 95:5, about 20:80 to about 80:20, about 40:60 to about 60:40, or about 50:50.

[0025] In such embodiments, at least two curable site monomers of the first curable perfluoropolymer may be present in the first curable perfluoropolymer in an amount of about 0.1 to about 10 mole percent, and at least one curable site monomer of the second curable perfluoropolymer may be present in the second curable perfluoropolymer in an amount of about 0.1 to about 10 mole percent. Furthermore, the curable sites of the at least two curable site monomers in the first curable perfluoropolymer may be nitrogen-containing curable sites. In such cases, the first curable perfluoropolymer may include a first curable site monomer containing a first cyano-curable site and a second curable site monomer containing a second cyano-curable site.

[0026] In the blended embodiment, at least one curing site in each of the at least two curing site monomers in the first curable perfluoropolymer can be selected from the group consisting of cyano, carboxyl, carbonyl, alkoxycarbonyl, and combinations thereof.

[0027] In the above-described method, the method may also include a step of incorporating at least one curing agent into the fluorine-containing elastomer composition before curing the composition, and in a preferred embodiment, at least two curing agents. Furthermore, the at least two curing agents may be present in the blended composition in a total amount of about 0.2 to about 10 parts by weight per 100 parts by weight of the curable perfluoropolymer in the composition. Furthermore, in such embodiments, each of the at least two curing agents may be present in the composition in an amount of about 0.1 to about 6 parts by weight per 100 parts by weight of the curable perfluoropolymer. Furthermore, in blended embodiments, the at least two curing agents may include a first curing agent present in the composition in an amount of about 0.5 to about 4 parts by weight per 100 parts by weight of the curable perfluoropolymer, and a second curing agent present in the composition in an amount of about 0.3 to about 2 parts by weight per 100 parts by weight of the curable perfluoropolymer. In one embodiment, the first curing agent is [ka] The second hardening agent is [ka] (In the formula, each R 1 These are independently -NH2, -NHR2, -OH, or -SH, and R 2 R is a monovalent organic group, 6 These are -SO2, -O-, -CO-, alkylene groups with 1 to about 6 carbon atoms, perfluoroalkylene groups with 1 to about 10 carbon atoms, single bonds or formula (IX): [ka] (It is a base as shown in [the diagram].) That is the case.

[0028] In a further embodiment, the second curing agent is given by formula (X): [ka] (In the formula, R 7 (Independently selected from hydrogen, alkyl groups of 1 to about 10 carbon atoms; partially fluorinated or perfluorinated alkyl groups of 1 to 10 carbon atoms; phenyl groups; benzyl groups; or phenyl or alkyl groups having a functional group (one or more) that is a lower alkyl or perfluoroalkyl group) It is a compound produced by [the company / organization].

[0029] In another preferred embodiment, the second curing agent may be bisaminophenol or a salt thereof.

[0030] The second curable perfluoropolymer may also contain curable site monomers having curable sites selected from the group consisting of halogens, nitrogen-containing groups, carboxyls, alkoxycarbonyls, and combinations thereof.

[0031] In another preferred embodiment, at least two types of curing agents are: [ka] Selected from the group consisting of bisaminophenol and combinations thereof.

[0032] In a more preferred embodiment, the first curing agent may be compound (XII) described in the claim, and the second curing agent may be bisaminophenol.

[0033] In one embodiment of a curable fluorine-containing elastomer composition, the composition may include a second curable fluoropolymer containing tetrafluoroethylene and at least one second fluorine-containing monomer, one of which is a curable site monomer containing at least one second curable site.

[0034] In such embodiments, the first curable fluoropolymer and / or the second curable fluoropolymer may be a perfluoropolymer, and the first curable fluoropolymer and the second curable fluoropolymer are preferably different.

[0035] The present invention further comprises a cured fluorine-containing elastomer formed by curing the curable fluorine-containing composition described above.

[0036] The present invention also includes molded articles formed by thermosetting and molding the compositions described above.

[0037] The present invention relates to a method for forming a fluoroelastomer product with reduced particulate matter, the method comprising the steps of: preparing a curable fluorine-containing elastomer composition comprising at least one curable fluoropolymer comprising at least one fluorine monomer and at least one fluorine-containing curing site monomer comprising at least one curing site; adding microdiamond particles having an average particle size of more than 0.10 microns to about 100 microns to the curable fluorine-containing elastomer composition; and curing the curable fluorine-containing elastomer composition to form a fluoroelastomer product, wherein when the fluoroelastomer product and the second fluoroelastomer product are exposed to a fluorine-based plasma, an oxygen-based plasma, a hydrogen-based plasma, or a combination thereof, the fluoroelastomer product has reduced particulate matter compared to a second fluoroelastomer product having the same fluorine-containing elastomer composition but without microdiamond particles.

[0038] In such a method, the curable fluorine-containing elastomer composition may further contain at least one filler, and the method may further include the step of adding microdiamond particles to the fluorine-containing elastomer composition while adding at least one filler to at least one first curable fluoropolymer.

[0039] In the method described above, at least one curable fluoropolymer may be a perfluoropolymer, the fluorinated monomer may be tetrafluoroethylene, at least one fluorine-containing curable site monomer may be a perfluorinated curable site monomer, and the perfluoropolymer may further contain a perfluoroalkyl vinyl ether.

[0040] The method described above may also include the step of incorporating a curing agent into the fluorine-containing elastomer composition before curing the composition.

[0041] In the above method, the fluoroelastomer product also preferably has a reduced compression set value at 250°C / 70 hours / 25% deflection compared to the second fluoroelastomer product. In such embodiments, the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product may further contain a carbon black filler.

[0042] In the above method, the fluoroelastomer product also preferably has reduced adhesion compared to the second fluoroelastomer product. In such embodiments, the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product may further contain a carbon black filler.

[0043] In the above method, the fluoroelastomer product preferably has improved resistance to fluorine-based plasma, oxygen-based plasma, hydrogen-based plasma, and combinations thereof, compared to the second fluoroelastomer product.

[0044] In the above method, the fluoroelastomer product preferably has further improved physical properties compared to the second fluoroelastomer product.

[0045] In the above method, the compression set value of the fluoroelastomer product at 350°C / 70 hours / 18% deflection is also preferably reduced compared to the second fluoroelastomer product. In such embodiments, the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product may further contain a carbon black filler.

[0046] The present invention also includes a method for forming a fluoroelastomer product having reduced compression set, the method comprising the steps of: preparing a curable fluorine-containing elastomer composition comprising at least one first curable fluoropolymer comprising at least one fluorine monomer and at least one fluorine-containing curing site monomer comprising at least one curing site; adding microdiamond particles having an average particle size of more than 0.10 microns to 100 microns to the curable fluorine-containing elastomer composition; and curing the curable fluorine-containing elastomer composition to form a fluoroelastomer product, wherein the fluoroelastomer product has a reduced compression set value at 250°C / 70 hours / 25% deflection compared to a second fluoroelastomer product formed from the same curable fluorine-containing elastomer composition but without microdiamond particles.

[0047] In this method, at least one curable fluoropolymer may be a perfluoropolymer, the fluorinated monomer is tetrafluoroethylene, at least one fluorine-containing curable site monomer may be a perfluorinated curable site monomer, and the perfluoropolymer may further contain a perfluoroalkyl vinyl ether.

[0048] The method described above may also include the step of incorporating a curing agent into the fluorine-containing elastomer composition before curing the composition.

[0049] In the above method, when the fluoroelastomer product and the second fluoroelastomer product are exposed to a fluorine-based plasma, an oxygen-based plasma, a hydrogen-based plasma, or a combination thereof, the fluoroelastomer product also preferably has reduced particulation compared to the second fluoroelastomer product. In such embodiments of the above method, the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product further comprises a carbon black filler.

[0050] In the above method, the fluoroelastomer product also preferably has reduced adhesion compared to the second fluoroelastomer product. In such embodiments, the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product may further contain a carbon black filler.

[0051] In the above method, the fluoroelastomer product also preferably has improved resistance to fluorine-based plasma, oxygen-based plasma, hydrogen-based plasma, and combinations thereof, compared to the second fluoroelastomer product.

[0052] In the above method, the fluoroelastomer product also preferably has improved physical properties compared to the second fluoroelastomer product.

[0053] In the above method, the compression set value of the fluoroelastomer product at 350°C / 70 hours / 18% deflection is also preferably reduced compared to the second fluoroelastomer product. In such embodiments of the above method, the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product may further contain a carbon black filler.

[0054] The present invention also includes a method for forming a fluoroelastomer product having reduced adhesion, comprising the steps of: preparing a curable fluorine-containing elastomer composition comprising at least one first curable fluoropolymer comprising at least one fluorine monomer and at least one fluorine-containing curing site monomer comprising at least one curing site; adding microdiamond particles having an average particle size of more than 0.10 microns to 100 microns to the curable fluorine-containing elastomer composition; and curing the curable fluorine-containing elastomer composition to form a fluoroelastomer product, wherein the fluoroelastomer product has reduced adhesion compared to a second fluoroelastomer product formed from the same curable fluorine-containing elastomer composition as the curable fluorine-containing elastomer but without microdiamond particles.

[0055] In the above method, at least one curable fluoropolymer may be a perfluoropolymer, the fluorinated monomer may be tetrafluoroethylene, at least one fluorine-containing curable site monomer may be a perfluorinated curable site monomer, and the perfluoropolymer may further contain a perfluoroalkyl vinyl ether.

[0056] The method described above may also include the step of incorporating a curing agent into the fluorine-containing elastomer composition before curing the composition.

[0057] In the above method, the fluoroelastomer product also preferably has a reduced compression set value at 250°C / 70 hours / 25% deflection compared to the second fluoroelastomer product. In such embodiments, the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product may further contain a carbon black filler.

[0058] In the above method, when the fluoroelastomer product and the second fluoroelastomer product are exposed to a fluorine-based plasma, an oxygen-based plasma, a hydrogen-based plasma, or a combination thereof, the fluoroelastomer product also preferably has reduced particulation compared to the second fluoroelastomer product. In such embodiments of the above method, the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product may further contain a carbon black filler.

[0059] In the above method, the fluoroelastomer product also preferably has improved resistance to fluorine-based plasma, oxygen-based plasma, hydrogen-based plasma, and combinations thereof, compared to the second fluoroelastomer product.

[0060] In the above method, the fluoroelastomer product also preferably has improved physical properties compared to the second fluoroelastomer product.

[0061] In the above method, the compression set value of the fluoroelastomer product at 350°C / 70 hours / 18% deflection is preferably reduced compared to the second fluoroelastomer product. In such embodiments, the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product may further contain a carbon black filler.

[0062] The present invention relates to a method for forming a fluoroelastomer product having reduced particulate matter, the method comprising the steps of: preparing a curable fluorine-containing elastomer composition comprising at least one curable fluoropolymer comprising at least one fluorine monomer and at least one fluorine-containing curing site monomer comprising at least one curing site; adding microdiamond particles having an average particle size of more than 0.10 microns to about 100 microns to the curable fluorine-containing elastomer composition; and curing the curable fluorine-containing elastomer composition to form a fluoroelastomer product, the method further comprising a method in which the fluoroelastomer product is usable at a usage temperature of at least about 350°C.

[0063] The method described above may also include the step of incorporating a curing agent into the fluorine-containing elastomer composition before curing the composition.

[0064] In the above method, the fluoroelastomer product may be a perfluoroelastomer product. In the above method, the fluoroelastomer product is preferably formed from the same curable fluorine-containing elastomer composition, but has a reduced compression set value at 350°C / 70 hours / 18% deflection compared to a second fluoroelastomer product that does not contain microdiamond particles. In such embodiments, the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product further comprises a carbon black filler. [Modes for carrying out the invention]

[0065] Detailed description of the invention As described in the background art section, prior art has shown that the use of diamond nanoparticles having a size greater than 0.1 microns typically results in a high defect rate associated with particle size reduction. The applicants have surprisingly found that the use of microdiamond particles greater than 0.1 microns results in lower particle size reduction than known competing plasma-resistant compositions. Furthermore, in preferred embodiments herein, such fillers also unexpectedly result in reduced compression set, reduced adhesion, improved resistance to fluorine-based plasmas, oxygen-based plasmas, hydrogen-based plasmas, and combinations thereof, as well as improved physical properties, even at high temperatures, and in more preferred embodiments, enable use at high operating temperatures along with reduced compression set.

[0066] The curable fluorine-containing elastomer composition comprises tetrafluoroethylene and at least one curable fluoropolymer containing at least one fluorine-containing monomer (one of which is a curable site monomer containing at least one curable site), as well as microdiamond particles. The curable fluorine-containing elastomer composition may also optionally incorporate at least one curing agent.

[0067] Preferred microdiamond particles have an average particle size of more than 0.1 microns to about 100 microns and may be synthetic microdiamonds, natural microdiamonds, or blends and combinations thereof. As used herein, “average particle size” is intended to mean the peak of the largest particle size curve characterizing the particle size distribution. When purchasing commercially available microdiamond particles, the seller usually indicates the average particle size, but such average particle size can be measured independently by any suitable method known or to be developed in the art. Preferred average particle sizes for achieving improved physical properties, as well as improved plasma resistance in, for example, NF3 and / or O2 and / or H plasmas, may be more than 0.1 microns to about 10 microns; more than 0.1 microns to about 5 microns; about 0.2 microns to about 2 microns; about 0.25 microns to about 1.0 microns and about 0.25 microns to about 0.5 microns, depending on the desired final properties and expected formulation in the particular polymer system, in various embodiments herein. In other preferred embodiments, an average particle size of about 2 to about 5 microns can be used for such plasma environments, while still achieving lower levels of particulation and unexpectedly low compression set values ​​even at higher temperatures, e.g., about 250°C and above, about 300°C and above, and about 350°C and above, compared to currently available compounds.

[0068] Microdiamond particles can have various shapes, including spherical particles, fibers, or flasks. Furthermore, the particles can exist in the form of agglomerated or aggregated structures. Suitable commercial-grade microdiamonds are available for use on polishing surfaces (e.g., on tools) from various suppliers, including The Dev Group, Dev Industrial Corp., Boca Raton, Florida, USA; Eastwind Diamond Abrasives of Vermont, USA; American Superabrasives, Florida, USA; Zhecheng Hongxiang Superhard Material Co., Ltd., China, and other manufacturers of polishing synthetic diamonds or synthetic or natural microdiamonds.

[0069] The composition may typically contain up to about 100 parts by weight of microdiamonds per 100 parts by weight of the base fluoropolymer or fluoropolymer used in the composition, but can be incorporated for various property effects. In some embodiments, the composition may preferably contain about 1 to about 50 parts by weight of microdiamonds per 100 parts by weight of the base fluoropolymer, or about 2 to about 20 parts per 100 parts by weight of the base fluoropolymer. The properties of microdiamonds enable excellent results and a good balance between physical and elastomeric properties at lower levels of about 0.5 to about 10 parts by weight, about 0.5 to about 5 parts by weight, or as low as about 2.75 to about 5 parts by weight per 100 parts by weight of the base curable fluoropolymer. It is also true that unexpectedly favorable or reduced levels of compression set can be achieved at preferred levels.

[0070] It is preferable to maintain the amount of filler at about 0.5 to about 50 parts per 100 parts of base fluoropolymer to avoid affecting the improved properties achieved herein and / or to achieve the benefits, taking into account the total amount of other typical fillers in such compositions. It should be noted that the goal for the compositions herein is to provide sufficient strength and physical properties without excessively negatively affecting elastomer properties, such as compression set, and / or, also preferably, to reduce adhesion and / or reduce particulate matter in products formed from the compositions, while improving plasma resistance in fluorine-based plasmas, oxygen-based plasmas, hydrogen-based plasmas, and combinations thereof. In attempting to achieve such goals, the compositions are further capable of functioning in such harsh environments and high temperatures, while in some cases improving compression set and enabling high operating temperatures. In this invention, such balanced properties can be achieved economically and advantageously with much lower concentrations of microdiamonds, so that compositions containing only about 1 to about 20 parts microdiamonds can yield excellent results, save on filler costs, and provide reduced particle size, reduced high-temperature compression set, reduced adhesion, improved plasma resistance in fluorine-based plasmas, oxygen-based plasmas, hydrogen-based plasmas, and combinations thereof, as well as improved physical properties.

[0071] Curable fluoropolymers are useful in harsher environments, such as those encountered in industrial use in oil fields or in the processing of petrochemicals, but in this case, any suitable curable fluoropolymer, including compositions suitable for use in clean environments, may be used. Curable fluoropolymers that can be used are materials classified by ASTM International according to the definition of standard rubber nomenclature provided in ASTM D1418-17. Standard FKM polymers according to such elastomer nomenclature typically have at least two monomers, one of which is fluorinated, preferably all of which are fluorinated to some extent, and have at least one curing site monomer for use in vulcanization. The at least two monomers preferably include vinylidene fluoride and hexafluoropropylene or similar fluorinated olefins, but may also include various other monomers known in the art or to be developed. Fluoroelastomer compositions may also include at least one curing agent capable of crosslinking with functional groups in the curing site monomers of the fluoroelastomer.

[0072] With respect to FKMs as used herein, such curable site monomers may include one curable site monomer that can be cured by a peroxide curing system. Such curable site monomers preferably have a functional group containing a halogenated material, such as Br or I, in the curable site functional group. At least two of the monomers in the FKM may be hexafluoropropylene (HFP) and vinylidene fluoride (VF2), but in addition to these two, other typical monomers may be used to form a variety of fluoropolymers known in the art, and the curable site monomers and curing systems may vary. "Peroxide curing system" means that a peroxide curing agent and any associated co-curing agent are used. Such systems are known in the art.

[0073] The curable fluoropolymer may be radiation crosslinkable, but preferably it is crosslinkable via a curing system (curable), and a curing agent is added that can react with functional groups in the curing site monomer to form an elastomer material. If necessary, at least one of a second curing agent, a cocuring agent, and / or a curing accelerator may also be used. The compositions herein may have a single curable fluoropolymer or a combination of at least two curable fluoropolymers, depending on the desired final properties, for example, in the form of a polymer blend, a graft composition, or an alloy.

[0074] The terms “uncured” or “curable” refer to fluoropolymers for use in the compositions herein that have not yet been subjected to any substantial degree of crosslinking reaction, and therefore the material has not yet been fully cured for its intended end use.

[0075] The curable fluoropolymers for the compositions herein may also include additional such polymers as needed in the blend-like compositions or graft / copolymerized compositions as described above. Furthermore, the polymer backbone may contain various curable site monomers along the chain that provide one or more different functional groups for crosslinking, preferably one of such groups for use in the present invention herein is curable by a peroxide curing system. The compositions may also contain curing agents and cocuring agents and / or accelerators to assist the crosslinking reaction. Additional curable sites and curing systems can be provided for the same or different curable site monomers, e.g., curable sites that react with a bisphenyl-based curing system to create crosslinks, e.g., curable sites having nitrogen-containing reactive groups, provided that peroxide-curable functional groups are also preferably present. Consequently, while this disclosure discusses various preferred curing agents (also referred to herein as crosslinking agents or curing agents), if additional curing sites known in the art are used, other curing agents capable of curing such alternative curing sites may also be used in addition to the preferred organic peroxide-based curing agents and co-curing agents herein. A further description of such curing systems is provided below.

[0076] One or more curable fluoropolymers may be present in such compositions. Such polymers are formed by polymerization or copolymerization of one or more fluorinated monomers. Such polymers can be formed using various techniques known in the art (such as direct polymerization, emulsion polymerization and / or free radical polymerization, latex polymerization, etc.).

[0077] Fluoropolymers can be formed by polymerizing two or more monomers, preferably one of which is at least partially fluorinated, but fully fluorinated monomers can also be used. For example, HFP and VF2 are preferably combined with tetrafluoroethylene (TFE) or one or more perfluoroalkyl vinyl ethers (PAVE), or similar monomers, together with at least one monomer that is a curing site monomer, i.e., at least one fluoropolymer curing site monomer, which enables curing. Fluoroelastomer compositions as described herein may include any suitable standard curable fluoroelastomer fluoropolymer (FKM) that can be cured to form a fluoroelastomer, preferably using a curing system as described herein and one or more other curing agents. Examples of suitable curable FKM fluoropolymers include those sold under the trademark name Tecnoflon® PL958, available from Solvay Solexis, SpA, Italy, or other similar fluoropolymers that, when used in the compositions herein, are preferably curable by a peroxide curing system. Other suppliers of such materials include Daikin Industries, Ltd., Japan, 3M Corporation, Minnesota, and EIDuPont de Nemours & Company, Inc., Delaware. Such FKM polymers are not fully fluorinated on the polymer backbone.

[0078] In preferred embodiments, particularly for end-use in high purity or clean environments, at least one first curable fluoropolymer is a curable perfluoropolymer useful for forming a perfluoroelastomer. The compositions herein, whether curable fluoropolymer compositions or perfluoropolymer compositions, may contain only one fluoropolymer or perfluoropolymer, or two or more such fluoropolymers or perfluoropolymers, and the compositions, when used and / or cured, may form a single fluoroelastomer or perfluoroelastomer, or, when two or more are used, a perfluoroelastomer blend composition. Furthermore, curable fluoropolymers can be blended with curable perfluoropolymers to produce partially fluorinated blended fluoroelastomers.

[0079] When used in this application, “perfluoroelastomer” or “cured perfluoroelastomer” includes, unless otherwise noted, any curable perfluoropolymer, for example, any cured elastomer material or composition formed by curing a preferred curable perfluoropolymer in the curable compositions described herein.

[0080] A “curable perfluoropolymer” (sometimes referred to in the art as a “perfluoroelastomer” or more appropriately as “perfluoroelastomer gum”) suitable for use in forming a cured perfluoroelastomer is substantially a completely fluorinated polymer, preferably completely perfluorinated on its polymer backbone. Based on this disclosure, it will be understood that, by using hydrogen as part of the crosslinking groups of functional groups, some residual hydrogen may be present in some perfluoroelastomers within the crosslinks of these materials. The cured material, e.g., a perfluoroelastomer, is a crosslinked polymer structure.

[0081] When used in the preferred perfluoroelastomer compositions herein, the curable perfluoropolymer that forms a cured perfluoroelastomer during curing is formed by polymerizing one or more perfluorinated monomers, one of which is preferably a perfluorinated curable site monomer having a curing site, i.e., a functional group that enables curing. The functional group may be a reactive group that is not perfluorinated, or may contain one. Two or more curable fluoropolymers or perfluoropolymers, and preferably at least one optional curing agent, can be combined in the compositions herein and then cured to form a resulting crosslinked, cured fluoroelastomer composition, preferably a perfluoroelastomer composition as described herein.

[0082] As used herein, a curable fluorine-containing elastomer composition may also be a curable perfluoropolymer composition, which is a blend and combination of two or more curable polymers, each of which is formed by polymerizing two or more perfluoropolymers, each containing at least one perfluorocurable site monomer having at least one functional group (curable site) that enables curing when perfluorolated. Such curable perfluoropolymer materials are also commonly referred to as FFKM, in accordance with the standardized rubber definition of the American Standardized Testing Methods (ASTM), the relevant parts of which are incorporated herein by reference, and as described herein in ASTM Standard D1418-17.

[0083] As used herein, “compression set” refers to the property of an elastomer material that remains deformed after the removal of a deformable compressive load and does not return to its original shape. The compression set value is expressed as a percentage of the original deflection from which the material cannot recover. For example, a compression set value of 0% indicates that the material completely returns to its original shape after the removal of the deformable compressive load. Conversely, a compression set value of 100% indicates that the material does not recover at all from the applied deformable compressive load. A compression set value of 30% means that 70% of the original deflection has been recovered. Higher compression set values ​​generally indicate a potential for seal leakage.

[0084] As described herein, the present invention includes curable fluorine-containing elastomer compositions, preferably curable perfluoroelastomer compositions, cured perfluoroelastomer compositions, and molded articles formed from such curable fluorine-containing elastomer compositions.

[0085] Such perfluoroelastomer compositions preferably comprise at least one, more preferably two or more curable perfluoropolymers, preferably perfluorocopolymers, of which at least one has a high tetrafluoroethylene (TFE) content. Other suitable comonomers may comprise other ethylenically unsaturated fluoromonomers. If two such perfluoropolymers are used in a blend, both preferably having TFE or another similar perfluorolated olefin monomer, at least one of the perfluoropolymers may be a high-TFE perfluoropolymer. Each polymer may also preferably have one or more perfluoroalkyl vinyl ethers (PAVEs), which may contain alkyl or alkoxy groups that may be linear or branched, and may also contain ether bonds. Preferred PAVEs for use herein include, for example, perfluoromethyl vinyl ether (PMVE), perfluoroethyl vinyl ether (PEVE), perfluoropropyl vinyl ether (PPVE), perfluoromethoxy vinyl ether, and other similar compounds. Particularly preferred PAVEs are PMVE, PEVE, and PPVE, with PMVE being the most preferred, as it provides excellent mechanical strength to the resulting product formed by curing the curable composition herein. PAVEs may be used alone or in combination with the PAVE types described above within the curable perfluoropolymer and in the final curable composition, insofar as their use is consistent with the present invention as described herein.

[0086] Preferred perfluoropolymers are copolymers of TFE, at least one PAVE, and at least one perfluorinated curable site monomer incorporating a curable site or functional group that enables crosslinking of the curable polymer. The curable site monomer may be of various types having the preferred curable sites described herein. Preferred curable sites are preferably nitrogen-containing groups, but other curable fluoropolymers or perfluoropolymers other than the first and / or second curable perfluoropolymer may be provided to the composition, so other curable site groups, such as carboxyl groups, alkylcarbonyl groups, or halogenated groups having, for example, iodine or bromine, as well as other curable sites known in the art, may also be used. Consequently, this disclosure provides herein the use of radiation curing or various preferred curing agents (also known herein as crosslinking agents or curing agents), but if other curable sites known in the art are used, other curing agents capable of curing such alternative curable sites may also be used. For example, peroxide curing systems, such as those based on organic peroxides, and related peroxide co-curing agents can be used together with halogenated functional group curing sites. It is most preferable that both the first and second perfluoropolymers contain nitrogen-containing curing sites.

[0087] Exemplary curing site monomers are listed below, which can be used in the curable fluoropolymers or curable perfluoropolymers described herein for use in curable compositions, most of which have a PAVE-based structure and contain reaction sites. The polymers may vary, but preferred structures are as follows: (A) CF2 = CFO(CF2CF(CF3)O) m (CF2) n -X 1 (A) (In the formula, m is an integer from 0 to 5, n is an integer from 1 to 5, X 1It has a nitrogen-containing group, for example, nitrile or cyano). However, carboxyl group, alkoxycarbonyl group or halogenated terminal group can also be X 1 and can be used as such.

[0088] Most preferably, the curing site monomer in any curable fluoropolymer or curable perfluoropolymer, or a blend of two curable perfluoropolymers of either or both of the first and second such curable perfluoropolymers is as described above (A) (where m is 0 and n is 5). The curing site or functional group X 1 described herein, for example, a nitrogen-containing group contains a reaction site for crosslinking when reacted with a curing agent. The compound according to formula (A) can be used alone or in various combinations thereof as required. From the viewpoint of crosslinking, the crosslinking functional group is preferably a nitrogen-containing group, preferably a nitrile group.

[0089] Further examples of the curing site monomer according to formula (A) include the following formulas (1) to (17): CY2=CY(CF2) n -X 2 (1) (where Y is H or F, and n is an integer from 1 to about 8) CF2=CFCF2R f 2 -X 2 (2) (where R f 2 is (-CF2) n -, -(OCF2) n -, and n is 0 or an integer from 1 to about 5) CF2=CFCF2(OCF(CF3)CF2) m (OCH2CF2CF2) n OCH2CF2-X 2 (3) (where m is 0 or an integer from 1 to about 5, and n is 0 or an integer from 1 to about 5) CF2=CFCF2(OCH2CF2CF2) m (OCF(CF3)CF2)n OCF(CF2)-X 2 (4) (In the formula, m is an integer between 0 and approximately 5, and n is an integer between 0 and approximately 5.) CF2 = CF(OCF2CF(CF3)) m O(CF2) n -X 2 (5) (In the formula, m is an integer between 0 and approximately 5, and n is an integer between 1 and approximately 8.) CF2 = CF(OCF2CF(CF3)) m -X 2 (6) (In the formula, m is an integer between 1 and approximately 5.) CF2 = CFOCF2(CF(CF3)OCF2) n CF(-X 2 )CF3(7) (In the formula, n is an integer between 1 and approximately 4.) CF2 = CFO(CF2) n OCF(CF3)-X 2 (8) (In the formula, n is an integer between 2 and approximately 5.) CF2 = CFO(CF2) n -(C6H4)-X 2 (9) (In the formula, n is an integer between 1 and approximately 6.) CF2 = CF(OCF2CF(CF3)) n OCF2CF(CF3)-X 2 (10) (In the formula, n is an integer between 1 and approximately 2.) CH2=CFCF2O(CF(CF3)CF2O) n CF(CF3)-X 2 (11) (In the formula, n is an integer between 0 and approximately 5.) CF2 = CFO(CF2CF(CF3)O) m (CF2) n =X 2 (12) (In the formula, m is an integer between 0 and approximately 4, and n is an integer between 1 and approximately 5.) CH2 = CFCF2OCF(CF3)OCF(CF3) - X 2(13) CH2=CFCF2OCH2CF2-X 2 (14) CF2 = CFO(CF2CF(CF3)O) m CF2CF(CF3)-X 2 (15) (In the formula, m is an integer greater than 0.) CF2 = CFOCF(CF3)CF2O(CF2) n -X 2 (16) (In the formula, n is an integer that is at least 1.) CF2 = CFOCF2OCF2CF(CF3))OCF2 - X 2 (17) (In the formula, X 2 This refers to the reaction site subunit of the monomer, for example, nitrile (-CN), carboxyl (-COOH), alkoxycarbonyl group [-COOR 5 (In the formula, R 5 (The group may be an alkyl group of 1 to about 10 carbon atoms, which may be fluorinated or perfluorinated), a halogen or alkylated halogen group (such as I or Br, CH2I, etc.). When a perfluorinated compound is used as a curing site monomer, it is preferable that the portion of the backbone of the curing site monomer that will be located within the polymer backbone chain does not contain hydrogen atoms. Such curing site monomers are used when excellent thermal resistance is desired for the perfluoroelastomer produced from the curing of a perfluoropolymer, and to prevent a decrease in molecular weight due to chain transfer when synthesizing a perfluoroelastomer by polymerization reaction. Furthermore, compounds having a CF2=CFO- structure are preferred from the viewpoint of providing excellent polymerization reactivity with TFE.

[0090] Suitable curing site monomers preferably include those having nitrogen-containing curing sites, such as nitrile or cyano curing sites, for favorable crosslinking reactivity. However, curing sites having carboxyl, alkoxycarbonyl, and COOH groups (with multiple and various skeletons in addition to those described above) and other similar curing sites known in the art and to be developed can also be used. Curing site monomers can be used alone or in various combinations.

[0091] Preferred perfluoropolymers that can be used herein contain TFE in a molar percentage of about 50 to about 95 mol percent of TFE in the perfluoropolymer compound. Such perfluoropolymers can also incorporate further comonomers, preferably perfluorinated, such as PAVEs, many of which are known in the art and can be used herein. Various PAVEs can be used in curable polymers for use in the compositions herein. In one embodiment, the curable site monomer may also be a perfluorinated curable site monomer having one or more curable site monomers, which may be cyano groups. In one embodiment, there may be two such curable site groups, for example, one curable site having a first cyano curable site group and the other having a second cyano curable site group.

[0092] Suitable perfluoropolymers are commercially available from Daikin Industries, Ltd. and described in U.S. Patent Nos. 6,518,366 and 6,878,778 and U.S. Published Patent Application No. 2008-0287627, which are incorporated herein by reference in the relevant portions relating to the perfluoropolymers described therein. Further commercially available perfluoropolymers for use in the preferred embodiments herein, comprising at least two curing site monomers, are available from Federal State Unitary Enterprise SVLebedev Institute of Synthetic Rubber of Petersburg, Russia or Lodestar, USA, as described in the scope of International Publication No. WO00 / 29479A1, which is incorporated herein by reference in the relevant portions relating to such perfluoroelastomers, as well as commercially available perfluoroelastomers from Federal State Unitary Enterprise SVLebedev Institute of Synthetic Rubber as PFK-65 or PFK-100.

[0093] In some embodiments of this specification, curable perfluoropolymers having a TFE content in the range of about 40 to about 80 mol percent and a PAVE content in the range of about 20 to about 60 mol percent may be used, and each curable site monomer may be present in an amount of about 0.1 to about 10 mol percent in total, or each may be present in an amount of about 0.1 to about 6 mol percent, or in a more preferred embodiment, the first curable site monomer may be present in an amount of about 0.2 to about 2.0 mol percent and the second curable site monomer may be present in an amount of about 0.5 to about 5.0 mol percent.

[0094] In some embodiments, two curable fluoropolymers are present in the blend, in which the polymer, for example, the polymer described above, may be the same as or different from the polymer described above, and can be used together with a second curable fluoropolymer or curable perfluoropolymer used herein, such second curable polymer may have, but not necessarily, the same content of TFE or PAVE. Preferably, a second perfluoropolymer may be used, which may be a fluoropolymer in which a fluororesin material is incorporated, for example, a fluororesin. Fluororesin particles can be provided in various forms and using various techniques. Fluororesins, for example, PTFE and its copolymers (FEP and PFA type polymers), core-shell or other modified fluoropolymers and in various sizes (microparticles, nanoparticles, etc.), each of these can be incorporated into the material by mechanical means or chemical treatment and / or polymerization, either alone or in combination. For example, known or to-be-developed technologies can be utilized, such as those described in U.S. Patent Nos. 4,713,418 and 7,476,711 (each of which is incorporated herein by reference with respect to such technologies), and other technologies such as those described in U.S. Patent No. 7,019,083, which is also incorporated herein by reference with respect to the use of fluoropolymer particles. Suitable commercially available polymers are available from 3M Corporation in St. Paul, Minnesota.

[0095] Examples of resulting elastomers formed therefrom using other perfluoropolymers and curing site monomers such as those described above can also be found in U.S. Patent Nos. 6,518,366, 6,878,778 and U.S. Published Patent Application No. 2008-0287627 and U.S. Patent No. 7,019,083, each of which is incorporated herein in the relevant portions relating thereto to the perfluoropolymers described therein, the resulting elastomers, and methods for forming them.

[0096] Perfluoropolymers for use in the compositions claimed herein can be synthesized using any known or to-be-developed polymerization techniques for forming fluorine-containing elastomers, including, for example, emulsion polymerization, latex polymerization, chain-initiated polymerization, batch polymerization, and others. Preferably, polymerization is carried out such that the reactive curing sites are located at either or both ends of the polymer backbone and / or depend on the main polymer backbone.

[0097] Uncured perfluoropolymers are commercially available and include perfluoropolymers sold under the name Dyneon® by 3M Corporation, St. Paul, Minnesota, Daiel-Perfluor®, and other similar polymers available from Daikin Industries, Ltd. (Osaka, Japan). Other preferred materials are also available from Solvay Solexis (Italy), Federal State Unitary Enterprise SV Lebedev Institute of Synthetic Rubber of Petersburg (Russia), Asahi Glass (Japan), and WLGore. Other examples of suitable perfluoropolymers and their blends can be found, for example, in U.S. Patents 9,018,309 and 9,365,712, which are incorporated herein by reference with respect to suitable perfluoropolymers and their blends.

[0098] Uncured perfluoropolymers can be cured by any method, including the use of radiation curing, but preferably contain at least one curing agent (also referred to herein as a crosslinking agent, curing agent and / or curing system) for use with various curable fluorine-containing elastomers, and the perfluoroelastomer compositions herein can be selected for use with various curing sites described herein and should be curable (i.e., reactable and crosslinkable), or otherwise undergo curing reactions with the curing sites or functional groups of the curing site monomers of various uncured perfluoropolymers in the composition to form crosslinks and produce an elastomer material in the form of a molded article.

[0099] Preferred crosslinking or curing agents are those that form crosslinks having oxazole, thiazole, imidazole, or triazine rings. Such compounds, as well as other curing agents including amidoxime, tetraamine, and amidorazone, can be used for crosslinking in the present invention.

[0100] For nitrogen-containing curing sites, preferred curing agents include bis-aminophenol and its salts and their combinations, as well as bisphenyl-based curing agents and their derivatives; bis-aminothiophenol, para-benzoquinone dioxime (PBQD), and various salts of such compounds. Examples of suitable curing agents can be found, for example, in U.S. Patents 7,521,510B2, 7,247,749B2, and 7,514,506B2, each of which is incorporated herein in the relevant sections concerning the enumeration of various curing agents for cyano-group-containing perfluoropolymers. In addition, perfluoropolymers can be cured using radiation curing techniques.

[0101] A more preferred curing agent for curing sites having cyano group curing sites is an aromatic amine having at least two crosslinkable groups, such as those of formulas (I) and (II) below, or a combination thereof, which forms a benzimidazole crosslinked structure upon curing. These curing agents are known in the art and are discussed in relevant parts and with specific examples in U.S. Patents 6,878,778 and 6,855,774, which are incorporated herein by reference. [ka] (In the formula, R 1 These are the same or different groups in formula (II), NH2, NHR 2 , OH, SH or monovalent organic group or other organic group, for example, alkyl, alkoxy, aryl, aryloxy, aralkyl and aralkyloxy groups having about 1 to about 10 carbon atoms, where the nonaryl group may be branched or linear and substituted or unsubstituted, R 2 The group may be -NH2, -OH, -SH, or a monovalent or other organic group, such as an aliphatic hydrocarbon group, a phenyl group, or a benzyl group, or an alkyl, alkoxy, aryl, aryloxy, aralkyl and aralkyloxy group, where each group has about 1 to about 10 carbon atoms, and the non-aryl group may be branched or linear and substituted or unsubstituted). Preferred monovalent or other organic groups, such as alkyl and alkoxy (or their perfluorinated versions), have 1 to 6 carbon atoms, and preferred aryl groups are phenyl and benzyl groups. Examples include -CF3, -C2F5, -CH2F, -CH2CF3 or -CH2C2F5, phenyl groups, benzyl groups; or phenyl or benzyl groups in which 1 to about 5 of the hydrogen atoms are substituted with fluorine atoms, e.g., -C6F5, -CH2C6F5 (wherein the formula the group may be further substituted with a group including -CF3 or other lower perfluoroalkyl groups), or phenyl or benzyl groups in which 1 to 5 hydrogen atoms are substituted with CF3, e.g., C6H 5-n(CF3) n -CH2C6H 5-n (CF3) n Examples include (wherein n is 1 to about 5). The hydrogen atom may be further substituted with a phenyl or benzyl group. However, phenyl and CH3 groups are preferred because they provide excellent thermal resistance, good crosslinking reactivity, and relatively simple synthesis.

[0102] A structure incorporating formula (I) or (II) into an organic amine should contain at least two such groups from formula (I) or (II) so as to yield at least two bridging reactive groups.

[0103] Curing agents having the following formulas (III), (IV), and (V) are also useful herein. [ka] (In the formula, R 3 Preferably SO, O or CO, or an organic or alkylene type group, such as an alkyl, alkoxy, aryl, aralkyl or aralkoxy group having 1 to 6 carbon atoms, or a perfluorinated version of such a group having about 1 to about 10 carbon atoms, being branched or linear, saturated or unsaturated, and being branched or linear (with respect to non-aryl type groups), or a single bond, R 4 Preferably, it is one of the following: [ka] It is a reactive side group, for example. [ka] (In the formula, R f 1 (i) is a perfluoroalkyl or perfluoroalkoxy group of about 1 to about 10 carbon atoms, which may be a linear or branched group, and / or may be saturated or unsaturated, and / or may be substituted or unsubstituted); and [ka] (In the formula, n is an integer between approximately 1 and approximately 10).

[0104] A single curing agent or a combination thereof can be selected from all curing agents specified herein within the scope of the present invention, depending on the curing site to be crosslinked. With respect to thermal resistance, crosslinking agents that form oxazole rings, imidazole rings, thiazole rings and triazine rings are preferred and may include compounds of the following formulas: (I), (II), (III), (IV), and (V), specifically formula (II) (wherein R 1 They are the same or different, and are -NH2 and -NHR respectively. 2 , -OH or -SH, R 2 is a monovalent organic group, preferably not hydrogen); formula (III) (wherein R 3 R is -SO2-, -O-, -CO-, and alkylene groups of 1 to about 6 carbon atoms, perfluoroalkylene groups of 1 to about 10 carbon atoms, or single bonds. 4 This is as described below); Equation (IV) (wherein R f 1 R is a perfluoroalkylene group with 1 to about 10 carbon atoms, and formula (V) (wherein n is an integer from 1 to about 10) is further discussed below. Among such compounds, the compound of formula (II) as described herein is preferred for its thermal resistance, where the thermal resistance is improved by the stabilization of the aromatic ring after crosslinking. 1 Regarding NR 2 Bond (where R 2 (is a monovalent organic group, not hydrogen) has higher oxidation resistance than the NH bond, so R 1 as - NHR 2 Using is also preferable.

[0105] A compound having at least two groups as shown in formula (II), and a compound having two to three crosslinkable reactive groups thereon, more preferably two crosslinkable groups, is preferred.

[0106] An exemplary curing agent based on the above preferred formula comprises at least two functional groups, for example, structural formulas (VI), (VII), or (VIII): [ka] (In the formula, R 5 (This represents a saturated or unsaturated, branched or linear, substituted or unsubstituted group, preferably consisting of about 1 to about 10 carbon atoms, perfluorinated with respect to a carbon atom; for example, alkyl, alkoxy, aryl, SO, O, CO, or similar groups.) [ka] (In the formula, R 1 This is as defined elsewhere in this specification, and R 6 (These may be O, SO2, CO, or an organic group that may be perfluorinated, such as an alkyl, alkoxy, aryl, aryloxy, aralkyl and aralkyloxy group having about 1 to about 10 carbon atoms, and the nonaryl group may be branched or linear, substituted or unsubstituted, or a single bond or an alkylene bond).

[0107] From the viewpoint of simple synthesis, in further embodiments preferred herein, the most preferred crosslinking agent is a compound having two crosslinkable reactive groups, such as that represented by formula (II), shown below in formula (VIII). [ka] (In the formula, R 1 As stated above, R 6 These are -SO2, -O-, -CO-, alkylene groups with 1 to about 6 carbon atoms, perfluoroalkylene groups with 1 to about 10 carbon atoms, single bonds or formula (IX): [ka] The group is as shown in (this formula provides an easier synthesis). Preferred examples of alkylene groups with 1 to about 6 carbon atoms are methylene, ethylene, propylene, butylene, pentylene, hexylene, etc. Examples of perfluoroalkylene groups with 1 to about 10 carbon atoms are, [ka] These compounds are well known as examples of bisaminophenyl compounds. A preferred compound with this structure is given by formula (X): [ka] [In the formula, R 7 In each case, these are the same or different, and each R 7 [This includes hydrogen, an alkyl group of 1 to about 10 carbon atoms; a partially fluorinated or perfluoroalkyl group of 1 to 10 carbon atoms; a phenyl group; a benzyl group; or a phenyl or benzyl group in which 1 to about 5 hydrogen atoms are replaced by fluorine or a lower alkyl group or a perfluoroalkyl group such as CF3.] This includes those.

[0108] Non-limiting examples of curing agents include 2,2-bis(2,4-diaminophenylhexafluoropropane), 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-phenylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-perfluorophenylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4(N-benzylamino)phenyl]hexafluoropropane, and similar compounds. Among these, preferred For excellent thermal resistance properties, 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, and 2,2-bis[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane are preferred. Tetraamines, such as 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[N1-phenyl-1,2-benzenediamine] or 2,2-bis[3-amino-4-(N-phenylaminophenyl)]hexafluoropropane are also preferred for their thermal resistance properties.

[0109] Other suitable curing agents, either known in the art or to be developed, include oxazole ring, imidazole ring, thiazole ring, and triazine ring forming curing agents, amidoxime and amidorazone crosslinking agents, and in particular bisaminophenol, bisaminophenol AF, and combinations thereof; bisaminothiophenol; bisamidine; bisamidoxime; bisamidrazone; monoamidine; monoamidoxime and monoamidrazone, examples of which are shown, for example, in U.S. Patents 7,247,749 and 7,521,510, which are incorporated by reference herein in the relevant parts, and include curing agents and co-curing agents and accelerators therein. The bisamidoxime, bisamidrazon, bisaminophenol, bisaminothiophenol, or bisdiaminophenyl curing agents are most preferred herein to react with nitrile or cyano groups, carboxyl groups, and / or alkoxycarbonyl groups in the perfluoropolymer to form perfluoroelastomers preferred in some embodiments herein, which in the resulting cured products formed from the compositions herein have oxazole rings, thiazole rings, imidazole rings, or triazine rings as crosslinks.

[0110] In one embodiment of this specification, a compound comprising at least two chemical groups having crosslinking reactive groups as in formula (I) or (II) can be used to increase thermal resistance and stabilize aromatic ring systems. It is preferable to have at least two such groups for each group in (I) or (II), as having fewer groups than two or three such groups may not result in sufficient crosslinking. Such combinations are known and are described in the applicant's U.S. Patents 9,018,309B2 and 9,365,712B2, which are incorporated herein by reference.

[0111] Such compositions are preferably blends of a first curable perfluoropolymer and a second curable perfluoropolymer in a ratio ranging from about 95:5 to about 5:95, preferably about 80:20 to about 20:80, and more preferably about 40:60 to about 60:40, or about 50:50.

[0112] Each of the at least one curing site monomers in each of the curable perfluoropolymers is preferably present in each of the first curable perfluoropolymer and the second curable perfluoropolymer in an amount of about 0.1 to about 10 mole percent.

[0113] If at least one curing agent is used, this curing agent may be present in a variable amount suitable for curing the curing site monomers of the curable perfluoropolymer in the composition, for example, in a total amount of about 0.2 parts by weight to about 10 parts by weight per 100 parts by weight of perfluoropolymer in the composition, and each may be present in an amount of about 0.1 to about 6 parts by weight per 100 parts by weight of perfluoropolymer in the composition, or preferably about 0.1 to about 2 parts by weight per 100 parts by weight of perfluoropolymer in the composition. In one embodiment, at least two curing agents are used in the first perfluoropolymer in an amount of about 0.5 to about 4 parts by weight per 100 parts by weight of perfluoropolymer relative to the first curing agent and about 0.3 to about 2 parts by weight per 100 parts by weight of perfluoropolymer relative to at least one second curing agent.

[0114] In either or both of the first and second curable perfluoropolymers, one curable site in at least one curable site monomer is preferably a nitrogen-containing curable site. The at least one curable site in at least one curable site monomer in the first curable perfluoropolymer can be selected from the group consisting of cyano, carboxyl, carbonyl, alkoxycarbonyl, and combinations thereof, and is most preferably a cyano group.

[0115] At least one curing agent is preferably one of the following suitable curing agents: imidoyl fluoride amidine; bisaminophenol; bisamidine; bisamidoxime; bisamidrazone; monoamidine; monoamidoxime; monoamidrazone; bisaminothiophenol; bisdiaminophenyl; formula (II):

Chem.

Chem.

Chem.

Chem.

Chem.

[0116] At least one curing agent is more preferably a curing agent of formula (II) (wherein R 1 -NHR 2 Aromatic amines having at least two crosslinkable groups represented by ); fluorimidoylamidines; bisaminophenols; and combinations thereof.

[0117] In one embodiment, the curable fluorine-containing elastomer composition preferably comprises at least one curing agent, which is a tetraamine compound within the range of compounds described above. Such compounds can be used alone or in combination. The compound most preferred to be used as a curing agent herein is formula (II) (wherein R 1 Ha-NHR 2 And R 2 This is due to the aryl group. Such compounds are also known as 4,4'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[N1-phenyl-1,2-benzenediamine] ("Nph-AF") (also known as "V6"). [ka]

[0118] In another embodiment herein, the most preferred curing agents relate to perfluoroimidoyl amidines, such as those found in U.S. Patent No. 8,362,167, which are incorporated by reference in relevant portions herein for the following compounds and similar compounds. One preferred compound, also described as DPIA-65, is also shown below herein. [Chemical formula] Other preferred compounds are bisaminophenols and their salts, and combinations thereof.

[0119] In a further embodiment, the composition is preferably a perfluoroelastomer composition and at least one curing agent comprises the use of Nph-AF (or V6): [Chemical formula] This compound can be used alone or in combination with another curing agent, for example, in combination with bisaminophenol or bisaminophenol AF, etc., and / or in combination with or as an alternative to these alternatives. At least one curing agent is DPIA-65: [Chemical formula] further comprises.

[0120] In other preferred embodiments herein, the compound of formula (XII) is used alone or [Chemical formula] (wherein each R 1 is independently -NH2, -NHR 2 , -OH or -SH, R 2 is a monovalent organic group, and R 6 is -SO2, -O-, -CO-, an alkylene group having 1 to about 6 carbon atoms, a perfluoroalkylene group having 1 to about 10 carbon atoms, a single bond or formula (IX): [ka] It is used in combination with a base such as those shown in [reference]. In such a combination, the second curing agent is preferably of formula (X): [ka] (In the formula, R 7 The first compound is independently selected from hydrogen, an alkyl group of 1 to about 10 carbon atoms, a partially fluorinated or perfluorinated alkyl group of 1 to 10 carbon atoms, a phenyl group, a benzyl group, or a phenyl or alkyl group having a functional group (one or more) that is a fluorinated or partially fluorinated phenyl group, a fluorinated or partially fluorinated benzyl group, or a lower alkyl or perfluoroalkyl group. The second curing agent in this combination is preferably bisaminophenol and its salts or a combination thereof.

[0121] In preferred embodiments, the preferred ratio of the curing agent of type XII to the bisaminophenol-type curing agent or related compound may be preferably about 0.5:1 to about 35:1, preferably about 1:1 to about 32:1, and most preferably about 2:1 to 15:1.

[0122] One preferred curable perfluoroelastomer composition for use with the microdiamond particles described above is a first curable perfluoropolymer comprising tetrafluoroethylene, a first perfluoroalkyl vinyl ether, and at least one first curable site monomer having at least one curable site monomer, or in a further embodiment, at least two curable site monomers, wherein the tetrafluoroethylene and the second perfluoroalkyl vinyl ether are present in varying amounts in the first curable perfluoropolymer and in at least one second curable site monomer having at least one curable site, and the second curable perfluoropolymer may incorporate therein, as necessary, fluorinated materials or other fillers, etc., and preferably further comprises at least one curing agent. The microdiamond particles can be incorporated into the polymer blend before or after blending the polymer and before or after incorporating any other fillers or additives, however, if the blended polymer is to be used, it is preferable that the polymer be blended before introducing the additives or fillers and / or microdiamond particles. Furthermore, in order to avoid premature curing, it is preferable to introduce any curing agent after other fillers and additives containing microdiamond particles, and before curing.

[0123] At least one type of hardener, [ka] The group can be selected from bisaminophenol, bisaminophenol AF, and combinations thereof, which include formula (XII) and combinations of bisaminophenol and / or its salts.

[0124] At least one of the curable site monomers in either the first or second curable perfluoropolymer preferably includes a nitrile group or other nitrogen-containing curable site, such as those described above.

[0125] In addition to the preferred curing agents described herein for use with fluorine-containing curable perfluoropolymers having nitrile groups, it is within the scope of the present invention to cure nitrile groups of the first and second perfluoropolymers and / or other perfluoropolymers added to the compositions herein using curing agents known in the art. Examples of other curing agents known in the art include, preferably, curing agents capable of forming triazine rings. When halogenated curing sites are utilized, peroxide curing agents and co-curing agents known in the art can also be used. Other suitable curing agents include those listed above.

[0126] Cured fluoroelastomers and perfluoroelastomer compositions, formed from curable fluoroelastomers or perfluoroelastomer compositions as described herein, can be cured and molded to form molded articles. Generally, the molded articles will be formed as sealing members such as O-rings, seals, gaskets, and inserts, but other shapes and uses known in the art or to be developed are envisioned herein.

[0127] A molded article can be bonded to a surface, for example, to form a bonded seal. Such bonded seals can be used, for example, to form pre-bonded doors, gates, and slit valve doors for use in semiconductor processing and other end applications. Surfaces to which such molded articles, such as seals, can be bonded include polymer surfaces as well as metal and metal alloy surfaces. In one embodiment, the present invention includes, for example, a gate or slit valve door formed from stainless steel or aluminum, to which an O-ring seal is matched with a groove in the door configured to receive the seal. Bonding can occur via the use of a bonding composition or via an adhesive.

[0128] The curable elastomer compositions described herein are first prepared by combining, for example, a blend of first and second perfluoropolymers, with at least one curable fluoropolymer or perfluoropolymer as described elsewhere herein.

[0129] The polymers can be combined using typical rubber processing equipment, such as open-roll mixers, Banbury mixers, and kneaders. The compositions can also be prepared using closed-type mixer methods. Preferably, a typical mixer is, for example, a two-rotor mixer, which is commonly used to combine fluoropolymers and other materials described. Preferably, in this method, the polymers, especially perfluoropolymers, are mixed at room temperature or at high temperatures of about 30°C to about 100°C, or about 50°C to about 250°C, depending on the type and design of the mixer.

[0130] If desired, although unnecessary, other additives may also be mixed into the composition, or added together with the microdiamond particles. Microdiamond particles can be incorporated at any point, but if a polymer blend is formed, they can be added after blending. Other additives are not required, but if desired, they may be added to alter certain properties. Examples of such additives include curing accelerators, co-curing agents, crosslinking aids, processing aids, plasticizers, fillers, etc., in the form of micropowder, pellets, fibers and nanopowder, such as silica, fluoropolymers as described above, such as TFE, fluorinated copolymers, core-shell modified fluoropolymers, fluorographite, silica, barium sulfate, carbon, carbon black, fluorocarbon, clay, talc, metal fillers (titanium oxide, aluminum oxide, yttrium oxide, silicon oxide, zirconium oxide), metal carbides (silicon carbide, aluminum carbide), metal nitrides (silicon nitride, aluminum nitride), and other inorganic fillers (aluminum fluoride). Examples of fillers include (aluminum, carbon fluoride), colorants, organic dyes and / or pigments, such as azo, isoindolenone, quinacridone, diketopyrrolopyrrole, anthraquinone, imide fillers (e.g., polyimides, polyamide-imides, and polyetherimides), ketone resins (e.g., polyarylene ketones such as PEEK, PEK, and PEKK), polyarylates, polysulfones, polyethersulfones, polyphenylene sulfides, polyoxybenzoates, etc., which may be used in amounts known in the art and / or may vary for different properties. All fillers described herein may be used alone or in combination with two or more such fillers and additives.

[0131] Preferably, any additives in at least one optional curing agent capable of curing cured sites on at least one first and / or second cured site monomer, including any curing accelerator, co-curing agent, crosslinking aid, etc., are added after other fillers, additives, and / or microdiamond particles have been incorporated into the fluoropolymer or perfluoropolymer.

[0132] The compositions herein may be highly filled, if desired, or may be formed without fillers. Additional fillers, as needed, such as those described above, may be used in a total amount of about 100 to about 150 parts per 100 parts of combined curable perfluoropolymer in the composition, and may be approximately this amount, especially if a higher level of microdiamond components is envisioned.

[0133] After combining a curable fluoropolymer or perfluoropolymer with an additive containing microdiamonds and / or any other necessary curing agent, the curable fluoropolymer or perfluoropolymer in the elastomer or perfluoroelastomer composition is cured to form a cured fluoroelastomer or perfluoroelastomer composition as described herein.

[0134] The curable composition is preferably cured for a temperature and time conventionally used, depending on the selected curing method or curing system, curing site and / or curing agent, to form the desired crosslinking bonds. The temperature should be sufficient to allow the curing reaction to proceed until the curable fluoropolymer or perfluoropolymer in the composition is substantially cured, preferably at least 90% or more. Preferred curing temperatures and times for preferred curable perfluoropolymer compositions are, for example, about 150°C to about 250°C and about 5 to about 40 minutes. After curing, a post-curing step may be used as needed. Acceptable post-curing temperatures and times for the most preferred perfluoropolymers described herein are, for example, about 200°C to about 320°C and about 5 to about 48 hours.

[0135] During curing, the curable compositions described herein can form into molded articles, but can also be cured using the heat and pressure applied to the mold. Preferably, the combined curable fluoropolymers and perfluoropolymers are formed into preformed articles such as extruded ropes, or other shapes useful for containing preformed articles in molds having grooves formed to accommodate preformed articles, and for forming molded articles during curing. Post-curing and bake-out, as needed, can also be carried out, preferably under air, nitrogen, or vacuum.

[0136] Further curing agents and curing accelerators for curing and / or accelerating the curing of curable polymers, either for acting in conjunction with the curing of fluoropolymers or perfluoropolymers, or for accelerating their curing, or as needed, may also be included herein. Examples of non-curable fluoropolymers or perfluoropolymers include those lacking reactive curing sites, and those formed from one or more ethylenically unsaturated monomers (e.g., TFE, HFP, and PAVE). Further curable perfluoropolymers may be any of the curable perfluoropolymers described herein, as well as those having curing sites suitable for crosslinking with organic peroxide curing systems known in the art, bisaminophenyl-based cured products, etc. Such polymers may also be added to develop alternative blends and to modify the properties of the compositions described herein.

[0137] The present invention also includes a method for forming a fluoroelastomer product having reduced particle size, reduced compression set and / or reduced adhesion, particularly at high temperatures, and preferably also having improved plasma resistance and improved physical properties in fluorine-based plasmas, oxygen-based plasmas, hydrogen-based plasmas, and combinations of such plasmas. The method includes the step of forming a fluoroelastomer product by preparing a curable fluorine-containing elastomer composition, for example, one curable fluoropolymer or perfluoropolymer having at least one fluorine monomer, e.g., VF2 or HFP, to a fluoropolymer alone or to tetrafluoroethylene, or to a perfluoropolymer, TFE, and other similar perfluorinated olefins and perfluoroalkyl vinyl ethers, each having at least one fluorine-containing curing site monomer (if depending on curing sites other than groups on VF2), and each such curing site monomer contains at least one curing site. Such a composition may also optionally contain at least one curing agent. The above method further comprises the steps of adding microdiamond particles having an average particle size of more than 0.1 microns to about 100 microns or other suitable particle sizes as described above to a curable fluorine-containing elastomer composition in the amount described above, and then curing the curable fluorine-containing elastomer composition to form a fluoroelastomer product.

[0138] In one embodiment, the curable fluorine-containing elastomer composition may contain at least one further additive / filler, e.g., carbon black or one of the above, and the method may further include the step of adding microdiamond particles to the fluorine-containing elastomer composition while adding at least one additive to the curable fluoropolymer or perfluoropolymer. It is understood from this disclosure that the microdiamond particles may be added before the addition of any fillers or additives as required as described above, but if one or more curing agents are used, these curing agents are preferably incorporated after the other additives and / or microdiamond particles have been incorporated into the fluoropolymer or perfluoropolymer.

[0139] In one embodiment of the above method, the composition cures to form a fluoroelastomer product, which, compared to a second similar fluoroelastomer product formed using the same fluorine-containing elastomer composition but without microdiamond particles, exhibits reduced particle size when both the fluoroelastomer product and the second fluoroelastomer product are exposed to a fluorine and / or oxygen and / or hydrogen-based plasma, or a combination thereof. Such low particle size is unexpectedly achieved in comparison to existing products marketed as plasma-resistant. In all methods described above and herein, the fluoroelastomer product may be a perfluoroelastomer product.

[0140] In the above method, it is also preferable that the compression set value of the fluoroelastomer product at 250°C / 70 hours / 25% deflection, and more preferably at 350°C / 70 hours / 18% deflection, is reduced compared to the second fluoroelastomer product, including cases where the second fluoroelastomer product is formed using a conventional filler, such as a carbon black filler.

[0141] It is also preferable that the fluoroelastomer product has reduced adhesion compared to the second fluoroelastomer product, including the case where a conventional filler is added to the second fluoroelastomer product. It is also preferable that the fluoroelastomer product having low particle size by the above method has improved plasma resistance and improved physical properties compared to the second fluoroelastomer product with respect to fluorine-based plasma, oxygen-based plasma, hydrogen-based plasma, and combinations thereof.

[0142] In one of the methods described herein, a curable fluorine-containing elastomer composition is prepared having at least one first curable fluoropolymer comprising at least one fluorine monomer and at least one fluorine-containing curing site monomer comprising at least one curing site, thereby forming a fluoroelastomer product having reduced compression set. The composition may also contain at least one curing agent as described in detail above. Microdiamond particles having an average particle size of more than 0.10 microns to 100 microns are added to the curable fluorine-containing elastomer composition. The fluorine-containing elastomer composition cures to form a fluoroelastomer product, which preferably has a reduced compression set value at 250°C / 70 hours / 25% deflection compared to a second fluoroelastomer product formed from the same curable fluorine-containing elastomer composition but without microdiamond particles, and preferably also has a reduced compression set value at 350°C / 70 hours / 18% deflection compared to the second fluoroelastomer product, and such benefits are further achieved even when conventional fillers, such as carbon black, are incorporated therein. Such high-temperature compression set values ​​demonstrate the ability to use the compositions of the present invention in end applications having high operating temperatures above about 200°C, above 300°C, or above 350°C.

[0143] When a fluoroelastomer product and a second fluoroelastomer product are exposed to a fluorine-based plasma, oxygen-based plasma, hydrogen-based plasma, or a combination thereof, it is preferable that the fluoroelastomer product also has reduced particulation compared to the second fluoroelastomer product, including when a conventional filler, such as carbon black, is incorporated into the second fluoroelastomer product. It is further possible that the formed fluoroelastomer product has reduced adhesion compared to the second fluoroelastomer product, improved resistance to fluorine-based plasma, oxygen-based plasma, hydrogen-based plasma, and combinations thereof, and improved physical properties compared to the second fluoroelastomer product, in any case these properties are beneficial even when a conventional filler is incorporated.

[0144] Another method described herein forms a fluoroelastomer product with reduced adhesion to avoid a situation in which the seal to be replaced cannot be easily removed from the part, which may require the use of tools that damage the generation of parts and particles in the system, and which may result in lost production time and worker costs. Economic and production benefits are achieved by reducing adhesion. In this method, a curable fluorine-containing elastomer composition is prepared, comprising at least one first curable fluoropolymer comprising at least one fluoride monomer and at least one fluorine-containing curing site monomer having at least one curing site. At least one curing agent may also be incorporated before curing as described above. Microdiamond particles are added to the curable fluorine-containing elastomer composition having an average particle size of more than 0.10 microns to 100 microns. The curable fluorine-containing elastomer composition cures to form a fluoroelastomer product, which is formed from the same curable fluorine-containing elastomer composition as the curable fluorine-containing elastomer, but has reduced adhesion compared to a second fluoroelastomer product that does not contain microdiamond particles.

[0145] In this method, the fluoroelastomer product also preferably has a reduced compression set value at 250°C / 70 hours / 25% deflection compared to the second fluoroelastomer product, and preferably the compression set value of the fluoroelastomer product at 350°C / 70 hours / 18% deflection is also reduced compared to the second fluoroelastomer product, respectively, including situations in which the second fluoroelastomer product also contains conventional fillers, such as carbon black. Preferably, in the above method, when the fluoroelastomer product and the second fluoroelastomer product are exposed to fluorine-based plasma, oxygen-based plasma, hydrogen-based plasma, and combinations thereof, the fluoroelastomer product has reduced particulation compared to the second fluoroelastomer product, improved resistance to fluorine-based plasma, oxygen-based plasma, hydrogen-based plasma, and combinations thereof, and improved physical properties compared to the second fluoroelastomer product, in either case this is beneficial, including in compositions incorporating conventional fillers.

[0146] The present invention is described below in conjunction with the following non-limiting examples. [Examples]

[0147] In the following examples, various components are used to evaluate the effects of different types and amounts of microdiamonds in perfluoroelastomer compositions. This is because such materials are known to lack the strength of other elastomers and are most likely to be subjected to harsh environments under clean conditions, such as semiconductor applications. Therefore, the ability to provide good physical and elastomeric properties that can withstand harsh materials, including fluorine and / or oxygen and / or hydrogen-based plasmas, e.g., NF3 and / or O2 and / or H plasmas, and preferably low adhesion, demonstrates that similar results can be achieved in such materials, along with low particle size, in other less demanding applications.

[0148] Example 1 In the first embodiment described herein, the composition of the present invention was tested in the same environment as a specific competing product currently marketed for use in such a plasma environment. The applicant's previous FFKM product described herein (Comparative Product A), which does not contain microdiamonds but instead uses polymer fillers, was used for comparative purposes, as well as a product from Daikin Industries, Ltd., known as Dupra® DU-3R1 (Comparative Product B), and a product from EIDuPont de Nemours, known as Kalrez® 9100 (Comparative Product C), among others. The exact composition of the competing products is not publicly known.

[0149] The compositions of the present invention were prepared using base perfluoropolymers and curing agents with different levels of microdiamonds (Examples 1 and 2). In all examples herein, the composition is presented as a percentage per 100 parts by weight of the base polymer (unless the weight of a separate base polymer is given).

[0150] In Examples 1 and 2, curable perfluoropolymers were used: Polymer A, available from Daikin Industries, Ltd. as GA-500PR; Polymer B, available from 3M Corporation, St. Paul Minnesota as Dyneon® PFE-133TB Z; and Polymer C, known as PFK-100 from Lodestar, USA, to the Federal State Unitary Enterprise SVLebedev Institute of Synthetic Rubber of Petersburg, Russia. The curing agents used in these examples have the following structure: [ka] The curing agent contained an imidoyl-based curing agent, DPIA-65, bisaminophenol (BOAP), and 4,4'-[2,2,2-trifluoro-l-(trifluoromethyl)ethylidene]bis[N1-phenyl-1,2-benzenediamine](Nph-AF), manufactured by Federal State Unitary Enterprise SVLebedev Institute of Synthetic Rubber, Petersburg, Russia. [ka] Such polymers are described in the polymer blends of U.S. Patent Nos. 9,018,309 and 9,365,712, which are incorporated herein by reference with respect to the formation of such polymers and blends.

[0151] A comparative example (Comparative Example D), which uses the same base polymer but does not contain microdiamonds, was also prepared as an unfilled composition, which is typically expected to have minimal particulation in harsh environments (however, the physical properties may or may not be sufficient depending on the unfilled composition).

[0152] Specific known formulations are shown in Table A below. Each composition was subjected to the same test procedure, and O-rings of similar size (214) were subjected to standardized plasma irradiation tests. A clean gas stream flowed through each component during circulation (60,000 cycles), entered a particle detector, and the particle count and size were determined. [Table A]

[0153] The particles measured using this test method ranged in size from 0.3 to 10 microns. As expected, unexposed samples generated very few particles. The samples were then exposed to circulating NF3 plasma in a test pack made of aluminum. After exposure and circulation, the particle size and count numbers collected throughout the circulation were processed.

[0154] During testing, plasma irradiation was found to produce process-induced damage, which was exacerbated by heating circulation. During testing, previous comparative products A and C had the highest particle counts, while Examples 1 and 2 of the present invention produced the fewest particles.

[0155] Example 2 Further tests were conducted to evaluate the effect on the compression set of thermal carbon black N990, a carbon black filler known for its use in the synthesis of elastomer compositions for making seals and the like, compared with various concentrations of microdiamonds. The microdiamonds used were manufactured by Eastwind Diamond Abrasives. These microdiamonds were also used in all of the following examples unless otherwise specified.

[0156] Compositions were prepared using the same base formulation but with different concentrations. In this example, two base curable perfluoropolymers were used, namely polymer C from Example 1 and polymer B from Example 1. The components of the compositions and the different amounts of carbon black or microdiamond additives are shown in Table B below, where Examples 3-9 of the present invention contained microdiamonds alone (i.e., Examples 8 and 9) or microdiamonds together with N990 (i.e., Examples 3-7), each in different amounts, while Comparative Examples G-J contained no microdiamond filler and only different amounts of N990.

[0157] The data shows that even smaller amounts of microdiamonds significantly reduce compression set levels at 250°C and 350°C compared to compositions containing only carbon N990. Since carbon fillers are known to increase compression set, this unexpected benefit of reduced compression set was not anticipated when adding carbon-based fillers, such as microdiamonds. Furthermore, it can be observed that when microdiamonds are incorporated, there is an unexpected benefit of reduced adhesion. Therefore, the compositions herein not only provide good physical properties while meeting the criteria for high-temperature use and reducing weight loss in the presence of NF3, O2, and / or H plasma, but they also provide the unexpected benefit of maintaining or significantly reducing compression set properties at 250°C and / or 350°C, and reducing the adhesion of elastomer compositions incorporating them. [Table B]

[0158] Example 3 For further micronization tests similar to those in Example 1, two compositions of the present invention, Examples 10 and 11, were prepared along with a control comparative example K. The components of the compositions are shown in Table C below, where polymer D is known as PFK-300 from Lodestar, USA, for the Federal State Unitary Enterprise SV Lebedev Institute of Synthetic Rubber of Petersburg (Russia), and the microdiamond powder had an average particle size of 0.250 microns and was manufactured by Eastwind Diamond Abrasives.

[0159] The compositions in Table C were tested by forming Test 214 O-rings for each of the three formulations (Comparative Example K, Example 10, and Example 11). The sample O-rings were exposed to a remote NF3 process at 250°C. The samples were then placed in a small valve and the valve was circulated at a rate of 1 cycle / 1.6 seconds. The samples were loaded into the valve and heated to 250°C. During circulation, clean, filtered air was drawn through the valve and supplied to a particle counter. Particle counts were collected throughout the entire test. The total particle counts at 36,000 seconds are shown in Table C. Comparative Example K, which did not contain fillers, had the highest total particle count. The compositions of the present invention demonstrated a significant reduction in particle size. [Table C]

[0160] Example 4 In this example, a plasma-resistant polymer (polymer D), the same curing agent, and a further compound, Example 12, containing somewhat fewer microdiamonds than in Example 10, were used to prepare a composition similar to that described in Example 3, as described in Table D below. The compositions were evaluated for their physical properties and their plasma resistance in fluorine-containing plasma (NF3) and oxygen-containing plasma (O2). Samples were tested, and improved physical properties, excellent compression set, and significantly improved resistance to the plasmas used were obtained even at higher concentrations of microdiamonds. [Table D]

[0161] Example 5 Compounds were prepared to evaluate the plasma resistance (measured by the decrease in weight percentage after plasma irradiation) of the resulting elastomer products using fluorine-based plasma (NF3) and oxygen-based plasma (O2). The compositions and test results are shown in Table E below. Compound samples for physical and plasma resistance testing were molded into test O-rings. Comparative Example L did not contain microdiamonds. Examples 13 and 14 were prepared using the same composition, which is a blend of polymers A and B used in Example 1, and these contained the curing agent NphAF described above, as used in Example 1, but each contained different levels of microdiamonds in the composition. [Table E]

[0162] The results show that, compared to the control, Examples 13 and 14 of the present invention maintained or improved overall physical properties and retained or improved compression set, while also reducing the level of weight loss from plasma irradiation of both fluorine-containing and oxygen-containing plasmas.

[0163] Example 6 In this example, Comparative Examples M, N, O, and P were prepared without microdiamonds, and Examples 15-21 of the present invention were prepared using curable perfluoropolymers, Tecnoflon® PFR 5910M (polymer E), Tecnoflon® PFR 5920M (polymer F), Tecnoflon® PFR 06HC (polymer G), and polymer D. Polymer D was used in the same synthesis examples of the present invention and used the same components as those included in Example 4, Table D, specifically Examples 10-12 of the present invention.

[0164] Examples 15-16 and Comparative Example M were prepared using polymer E and peroxide curing agent Varox® DBPH together with the examples of the present invention having different amounts of microdiamonds.

[0165] Examples 17 and 18 of the present invention, as well as Comparative Example N, were prepared using polymer F and Varox® DBPH, along with different amounts of microdiamonds in Examples 17 and 18.

[0166] Examples 19 and 20 of the present invention, as well as Comparative Example O, were prepared using a blend of polymers E and F and Varox® DBPH, along with different amounts of microdiamonds in Examples 19 and 20.

[0167] Example 21 was prepared using polymer G with a PTFE lubricant, PTFE L5F, and a peroxide curing system containing Varox® DBPH and DIAK#7. While the control and comparative example P did not contain microdiamonds, Example 21 contained 5 parts microdiamonds per 100 parts of the base polymer, polymer G. The composition is shown in Table F below.

[0168] All compositions were subjected to different levels of hydrogen-containing plasma using the plasma irradiation test described above. Thus, pure hydrogen plasma (100% hydrogen) and blends of hydrogen plasma with fluorine-containing plasma (CF4), oxygen-containing plasma (O2), and nitrogen-containing plasma (N2) were prepared. The plasma was supplied to the test at a pressure of 600 mT, power of 300 W, and temperature of 200 °C in all cases, and applied for 1 hour. The blended plasmas used contained varying amounts of hydrogen plasma within the plasma delivered to the test: 100% for pure hydrogen plasma irradiation, 70% for the blend with nitrogen-containing plasma, and 50% for the blends with fluorine-containing plasma and oxygen-containing plasma.

[0169] After exposure to these different plasmas, in all cases, the weight loss reduced for the examples of the present invention was less than that of comparative examples having the same formulation but lacking microdiamonds. In addition, in the examples of the present invention, the weight loss decreased as the microdiamond content increased. Weight loss data for different plasmas and examples can also be found in Table F. These results were true for each of the cured perfluoroelastomer products tested, each using perfluoropolymers already utilized for end-use applications demonstrating high levels of chemical or plasma resistance and low particle size reduction. Even when such polymers were used in an unfilled or clean-filled state, the weight loss in plasma was reduced. [Table F]

[0170] Example 7 To further evaluate the physical properties and plasma resistance characteristics derived from the present invention as described herein, compositions were prepared using polymer G with or without microdiamonds. Samples were prepared as described above and tested for physical properties, compression set, and plasma resistance in both nitrogen-containing plasma (NF3) and oxygen-containing plasma (O2). The compositions and test results are shown in Table G for both Comparative Example Q and Example 22 of the present invention. [Table G]

[0171] The test results again indicate that in compositions exhibiting very good properties for use in semiconductor or similar applications requiring low particle size, good physical properties, and high levels of plasma resistance, all of these properties were maintained or improved by the use of microdiamonds, as in the case of compression set.

[0172] Example 8 Additional tests were conducted using different amounts of Technoflon® PFR X1065O (Polymer I) and Technoflon® X1075O (Polymer J). Each of these is a Tecnoflon® FFKM, manufactured by Solvay®, for use in applications requiring heat and chemical resistance. Polymer I was used alone and in blends with Polymer J. These were cured with BOAP, and the compounds cured in Comparative Examples R, S, and T did not contain microdiamonds. In Examples 23 - 28 of the present invention, different amounts of microdiamonds were incorporated. The compositions were molded into test specimens at 170 °C for 20 minutes and post-cured in air at 290 °C for 8 / 16 hours. The specimens were all tested with respect to these physical properties, as well as their compression set and their resistance to nitrogen-containing plasma (NF3) and oxygen-containing plasma (O2). Data for all tests and compositions are shown in Table H below. Comparison of the different compositions demonstrated that, in all cases, regardless of the combination of polymers and formulations used, the physical properties were retained or improved, the compression set remained approximately the same, and the weight loss in plasma was significantly reduced.

Table H-1

Table H-2

[0173] Example 9 Based on the use of a commercially available polymer, Tecnoflon® P959, manufactured by Solvay (Polymer H), a fluoroelastomer (FKM) composition was prepared. The polymer was cured using a peroxide curing system based on Varox® DBPH and DIAK #7. In Comparative Example U, no microdiamond was provided, and in Examples 29 and 30 of the present invention, various amounts of microdiamond were incorporated into the composition. Using a mixer, the composition was milled at 120°F, molded at 310°F for 10 minutes, and post-cured at 450°F in air for 30 - 2 - 45 hours. Similar to the various FFKM examples described above, in FKM, the same effects are seen, the physical properties are improved, and the compression set is the same or improved. In this example, the compression set is substantially improved. Furthermore, the adhesion is also reduced, which is a further advantage in many end uses. The composition and test results are included in Table I below.

Table I

[0174] Those skilled in the art will understand that modifications can be made to the embodiments described above without departing from the broad concept of the present invention. Therefore, it should be understood that the present invention is not limited to the specific embodiments disclosed, but is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims. The present invention provides, for example, the following items: (Item 1) A curable fluorine-containing elastomer composition comprising at least one curable fluoropolymer containing at least one fluorinated monomer and at least one fluorine-containing curable site monomer containing at least one curable site, and microdiamond particles having an average particle size of more than 0.10 microns to about 100 microns. (Item 2) The curable fluorine-containing elastomer composition according to item 1, wherein the microdiamond particles have an average particle size of more than 0.1 microns to about 10 microns. (Item 3) The curable fluorine-containing elastomer composition according to item 2, wherein the microdiamond particles have an average particle size of more than approximately 0.1 microns to approximately 5 microns. (Item 4) The curable fluorine-containing elastomer composition according to item 2, wherein the microdiamond particles have an average particle size of about 0.20 microns to about 2 microns. (Item 5) The curable fluorine-containing elastomer composition according to item 4, wherein the microdiamond particles have an average particle size of about 0.25 microns to about 1 micron. (Item 6) The curable fluorine-containing elastomer composition according to item 1, wherein the microdiamond particles have an average particle size of about 0.25 microns to about 0.5 microns. (Item 7) The curable fluorine-containing elastomer composition according to item 1, wherein the microdiamond particles have a shape selected from spherical particles, fibers, or flasks. (Item 8) The curable fluorine-containing elastomer composition according to item 1, wherein the microdiamond particles are natural microdiamond particles. (Item 9) The curable fluorine-containing elastomer composition according to item 1, wherein the microdiamond particles are synthetic microdiamond particles. (Item 10) The curable fluorine-containing elastomer composition according to item 1, wherein the microdiamond particles are a blend of natural microdiamond particles and synthetic microdiamond particles. (Item 11) The curable fluorine-containing elastomer composition according to item 1, wherein the particles exist in the form of agglomerated or aggregated masses. (Item 12) The curable fluorine-containing elastomer composition according to item 1, wherein the composition contains about 0.1 to about 100 parts by weight of microdiamond particles per 100 parts by weight of at least one curable fluoropolymer. (Item 13) The curable fluorine-containing elastomer composition according to item 12, wherein the composition comprises about 1 to about 50 parts of microdiamond particles per 100 parts by weight of at least one curable fluoropolymer. (Item 14) The curable fluorine-containing elastomer composition according to item 13, wherein the composition comprises about 2 to about 20 parts of microdiamond particles per 100 parts by weight of at least one curable fluoropolymer. (Item 15) The curable fluorine-containing elastomer composition according to item 1, wherein the at least one curable fluoropolymer is a curable perfluoropolymer, the at least one fluorinated monomer is tetrafluoroethylene, the perfluoropolymer further comprises a perfluoroalkyl vinyl ether monomer, and the at least one fluorine-containing curable site monomer is a perfluorinated curable site monomer. (Item 16) A curable fluorine-containing elastomer composition according to item 15, further comprising at least one curing agent. (Item 17) The curable fluorine-containing elastomer composition according to item 16, wherein the curing agent is a peroxide curing type. (Item 18) The curable fluorine-containing elastomer composition according to item 1, wherein the at least one curable fluoropolymer is a curable perfluoropolymer, the at least one fluorinated monomer is tetrafluoroethylene, the curable perfluoropolymer further comprises a perfluoroalkyl vinyl ether monomer, and the curable perfluoropolymer contains fluororesin particles therein. (Item 19) A curable fluorine-containing elastomer composition according to item 18, further comprising at least one curing agent. (Item 20) The curable fluorine-containing elastomer composition according to item 19, wherein the curing agent is a peroxide curing type. (Item 21) The curable fluorine-containing elastomer composition according to item 1, wherein the curable fluoropolymer is a perfluoropolymer, the at least one fluorinated monomer is tetrafluoroethylene, and the perfluoropolymer further comprises a perfluoroalkyl vinyl ether monomer, each having at least one curable site, and there are at least two fluorine-containing curable site monomers. (Item 22) A curable fluorine-containing elastomer composition according to item 21, further comprising at least one curing agent. (Item 23) The curable fluorine-containing elastomer composition according to item 22, wherein one of the curing agents is a peroxide curing type. (Item 24) The curable fluorine-containing elastomer composition according to item 22, wherein the composition comprises a blend of a curable perfluoropolymer having a second curable perfluoropolymer containing tetrafluoroethylene, a second perfluoroalkyl vinyl ether monomer, and a perfluorinated curing site monomer, wherein the second perfluoropolymer contains fluororesin particles, and the composition further comprises at least two curing agents. (Item 25) A curable fluorine-containing elastomer composition according to item 24, wherein the weight percentage ratio of the first curable perfluoropolymer to the weight of the second curable perfluoropolymer is in the range of about 5:95 to about 95:5. (Item 26) The curable fluorine-containing elastomer composition according to item 25, wherein the range of the ratio of the first curable perfluoropolymer by weight to the second curable perfluoropolymer is about 20:80 to about 80:20. (Item 27) The curable fluorine-containing elastomer composition according to item 26, wherein the range of the ratio of the first curable perfluoropolymer by weight to the second curable perfluoropolymer is about 40:60 to about 60:40. (Item 28) The curable fluorine-containing elastomer composition according to item 27, wherein the range of the ratio of the first curable perfluoropolymer by weight to the second curable perfluoropolymer is about 50:50. (Item 29) The curable fluorine-containing elastomer composition according to item 24, wherein each of the at least two curable site monomers of the first curable perfluoropolymer is present in the first curable perfluoropolymer in an amount of about 0.1 to about 10 mole percent, and the at least one curable site monomer of the second curable perfluoropolymer is present in the second curable perfluoropolymer in an amount of about 0.1 to about 10 mole percent. (Item 30) The curable fluorine-containing elastomer composition according to item 24, wherein the curable sites in at least two curable site monomers in the first curable perfluoropolymer are nitrogen-containing curable sites. (Item 31) The curable fluorine-containing elastomer composition according to item 30, wherein the first curable perfluoropolymer comprises a first curable site monomer including a first cyanocurable site and a second curable site monomer including a second cyanocurable site. (Item 32) The curable fluorine-containing elastomer composition according to item 24, wherein at least one curable site in each of the at least two curable site monomers in the first curable perfluoropolymer is selected from the group consisting of cyano, carboxyl, carbonyl, alkoxycarbonyl, and combinations thereof. (Item 33) The curable fluorine-containing elastomer composition according to item 24, wherein at least two curing agents are present in the composition in a total amount of about 0.2 to about 10 parts by weight per 100 parts by weight of the curable perfluoropolymer in the composition. (Item 34) The curable fluorine-containing elastomer composition according to item 24, wherein each of the at least two curing agents is present in the composition in an amount of about 0.1 parts by weight to about 6 parts by weight per 100 parts by weight of the curable perfluoropolymer. (Item 35) The curable fluorine-containing elastomer composition according to item 24, wherein the at least two curing agents include a first curing agent present in the composition in an amount of about 0.5 parts by weight to about 4 parts by weight per 100 parts by weight of the curable perfluoropolymer, and a second curing agent present in the composition in an amount of about 0.3 parts by weight to about 2 parts by weight per 100 parts by weight of the curable perfluoropolymer. (Item 36) The first curing agent is

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Claims

1. A curable fluorine-containing elastomer composition comprising at least one curable fluoropolymer and microdiamond particles having an average particle size of more than 0.10 microns to about 100 microns, The at least one curable fluoropolymer is (i) at least one curable fluoropolymer comprising at least two fluorinated monomers, wherein (a) one of the at least two fluorinated monomers is a fluorinated olefin or a perfluoroalkyl vinyl ether, and (b) the other of the at least two fluorinated monomers is vinylidene fluoride or at least one fluorine-containing curable site monomer comprising at least one curable site, and (ii) (a) at least one curable perfluoropolymer comprising at least one perfluoro monomer selected from perfluoroolefin monomers and perfluoroalkyl vinyl ether monomers, and (b) at least one perfluorofluorine-containing curable site monomer comprising at least one curable site. Selected from, When the composition is cured, a fluoroelastomer or perfluoroelastomer having reduced particle size and improved plasma resistance is formed. A curable fluorine-containing elastomer composition.

2. The curable fluorine-containing elastomer composition according to claim 1, wherein the microdiamond particles have an average particle size of more than 0.1 microns to about 10 microns.

3. The curable fluorine-containing elastomer composition according to claim 2, wherein the microdiamond particles have an average particle size of more than 0.1 microns to about 5 microns.

4. The curable fluorine-containing elastomer composition according to claim 2, wherein the microdiamond particles have an average particle size of about 0.20 microns to about 2 microns.

5. The curable fluorine-containing elastomer composition according to claim 4, wherein the microdiamond particles have an average particle size of about 0.25 microns to about 1 micron.

6. The curable fluorine-containing elastomer composition according to claim 1, wherein the microdiamond particles have an average particle size of about 0.25 microns to about 0.5 microns.

7. The curable fluorine-containing elastomer composition according to claim 1, wherein the microdiamond particles have a shape selected from spherical particles, fibers, or flasks.

8. The curable fluorine-containing elastomer composition according to claim 1, wherein the microdiamond particles are natural microdiamond particles or synthetic microdiamond particles.

9. The curable fluorine-containing elastomer composition according to claim 1, wherein the microdiamond particles are a blend of natural microdiamond particles and synthetic microdiamond particles.

10. The curable fluorine-containing elastomer composition according to claim 1, wherein the particles exist in the form of agglomerated or aggregated masses.

11. The curable fluorine-containing elastomer composition according to claim 1, wherein the composition comprises about 0.1 to about 100 parts by weight of microdiamond particles per 100 parts by weight of at least one curable fluoropolymer.

12. The curable fluorine-containing elastomer composition according to claim 11, wherein the composition comprises about 1 to about 50 parts by weight of microdiamond particles per 100 parts by weight of at least one curable fluoropolymer.

13. The curable fluorine-containing elastomer composition according to claim 12, wherein the composition comprises about 2 to about 20 parts by weight of microdiamond particles per 100 parts by weight of at least one curable fluoropolymer.

14. The curable fluorine-containing elastomer composition according to claim 1, wherein the at least one curable fluoropolymer is the at least one curable perfluoropolymer, and the at least one perfluorinated monomer comprises tetrafluoroethylene and the at least one perfluoroalkyl vinyl ether monomer.

15. The curable fluorine-containing elastomer composition according to claim 14, further comprising at least one curing agent, wherein the curing agent is optionally a peroxide curing system.

16. The curable fluorine-containing elastomer composition according to claim 1, wherein the at least one curable fluoropolymer is the at least one curable perfluoropolymer, the at least one perfluorinated monomer comprises tetrafluoroethylene and the at least one perfluoroalkyl vinyl ether monomer, and the curable perfluoropolymer contains fluororesin particles therein.

17. The curable fluorine-containing elastomer composition according to claim 16, further comprising at least one curing agent, wherein the curing agent is optionally a peroxide curing system.

18. The curable fluorine-containing elastomer composition according to claim 1, wherein the at least one curable fluoropolymer is the at least one curable perfluoropolymer, the at least one curable perfluoropolymer is a first curable perfluoropolymer, the at least one perfluorinated monomer is tetrafluoroethylene, and the first curable perfluoropolymer further comprises the at least one perfluoroalkyl vinyl ether monomer, each having at least one curable site, and there are at least two perfluorinated fluorine-containing curable site monomers.

19. The curable fluorine-containing elastomer composition according to claim 18, further comprising at least one curing agent, wherein one of the curing agents is optionally a peroxide curing system.

20. The curable fluorine-containing elastomer composition according to claim 19, wherein the composition comprises a blend of the first curable perfluoropolymer and a second curable perfluoropolymer comprising tetrafluoroethylene, a second perfluoroalkyl vinyl ether monomer and a perfluorinated curing site monomer, wherein the second perfluoropolymer contains fluororesin particles, and the composition further comprises at least two curing agents.

21. The curable fluorine-containing elastomer composition according to claim 20, wherein the weight percentage ratio of the first curable perfluoropolymer to the weight of the second curable perfluoropolymer is in the range of about 5:95 to about 95:5, or about 20:80 to about 80:20, or about 40:60 to about 60:40, or about 50:

50.

22. The curable fluorine-containing elastomer composition according to claim 20, wherein each of the at least two perfluorinated fluorine-containing curable site monomers of the first curable perfluoropolymer is present in the first curable perfluoropolymer in an amount of about 0.1 to about 10 mole percent, and the at least one perfluorinated curable site is present in the second curable perfluoropolymer in an amount of 10 mole percent.

23. The curable fluorine-containing elastomer composition according to claim 20, wherein the curable sites in at least two of the perfluorofluorine-containing curable site monomers in the first curable perfluoropolymer are nitrogen-containing curable sites, and the nitrogen-containing curable sites may, if necessary, be a first cyano-curable site on a first curable site monomer of the first curable perfluoropolymer and a second cyano-curable site on a second curable site monomer of the first curable perfluoropolymer.

24. The curable fluorine-containing elastomer composition according to claim 20, wherein at least one curable site in each of the at least two perfluorinated fluorine-containing curable site monomers in the first curable perfluoropolymer is selected from the group consisting of cyano, carboxyl, carbonyl, alkoxycarbonyl, and combinations thereof.

25. The curable fluorine-containing elastomer composition according to claim 20, wherein the at least two curing agents are present in the composition in an amount of about 0.2 to about 10 parts by weight per 100 parts by weight of the blend of the first curable perfluoropolymer and the second curable perfluoropolymer, and optionally in an amount of about 0.1 to about 6 parts by weight per 100 parts by weight of the blend of the first curable perfluoropolymer and the second curable perfluoropolymer in total.

26. The curable fluorine-containing elastomer composition according to claim 20, wherein the at least two curing agents include a first curing agent present in the composition in an amount of about 0.5 parts by weight to about 4 parts by weight per 100 parts by weight of the blend of the first curable perfluoropolymer and the second curable perfluoropolymer, and a second curing agent present in the composition in an amount of about 0.3 parts by weight to about 2 parts by weight per 100 parts by weight of the blend of the first curable perfluoropolymer and the second curable perfluoropolymer.

27. The first curing agent is 【Chemistry 32】 The second curing agent is, 【Transformation 33】 (In the formula, each R １ It is independently, -NH ２ , - NHR ２ , -OH or -SH, R ２ is a monovalent organic group, R ６ is, -SO ２ -O-, -CO-, alkylene group with 1 to about 6 carbon atoms, perfluoroalkylene group with 1 to about 10 carbon atoms, single bond or formula (IX): 【Transformation 34】 (It is a base as shown in [reference].) The curable fluorine-containing elastomer composition according to claim 20.

28. The second curing agent is given by formula (X): 【Chemistry 35】 (In the formula, R ７ (Independently selected from hydrogen, alkyl groups of 1 to about 10 carbon atoms; partially fluorinated or perfluorinated alkyl groups of 1 to 10 carbon atoms; phenyl groups; benzyl groups; or fluorinated or partially fluorinated phenyl groups; fluorinated or partially fluorinated benzyl groups; or phenyl or alkyl groups having one or more functional groups that are lower alkyl or perfluoroalkyl groups.) The curable fluorine-containing elastomer composition according to claim 27, wherein the compound is a compound thereof, and the second curing agent is optionally bisaminophenol or a salt thereof.

29. The curable fluorine-containing elastomer composition according to claim 20, wherein the second curable perfluoropolymer comprises a curable site monomer having a curable site selected from the group consisting of halogens, nitrogen-containing groups, carboxyls, alkoxycarbonyls, and combinations thereof.

30. The at least two curing agents described above are 【Transformation 36】 A curable fluorine-containing elastomer composition according to claim 20, selected from the group consisting of bisaminophenol and combinations thereof.

31. A cured fluorine-containing elastomer formed by curing the curable fluorine-containing composition described in claim 1.

32. A molded article formed by thermosetting and molding the composition described in claim 1.

33. A method for forming a fluoroelastomer product having reduced particulate matter, wherein the method is A step of preparing a curable fluorine-containing elastomer composition comprising at least one curable fluoropolymer, wherein the at least one curable fluoropolymer is (i) at least one curable fluoropolymer comprising at least two fluorinated monomers, wherein (a) one of the at least two fluorinated monomers is a fluorinated olefin or a perfluoroalkyl vinyl ether, and (b) the other of the at least two fluorinated monomers is vinylidene fluoride or at least one fluorine-containing curable site monomer comprising at least one curable site, and (ii) (a) at least one curable perfluoropolymer comprising at least one perfluoro monomer selected from perfluoroolefin monomers and perfluoroalkyl vinyl ether monomers, and (b) at least one perfluorofluorine-containing curable site monomer comprising at least one curable site. The selected step from, The steps include adding microdiamond particles having an average particle size of more than 0.10 microns to about 100 microns to the curable fluorine-containing elastomer composition, A method comprising the steps of curing the curable fluorine-containing elastomer composition to form the fluoroelastomer product, wherein, when the fluoroelastomer product and the second fluoroelastomer product are exposed to at least one of a fluorine-based plasma, an oxygen-based plasma, a hydrogen-based plasma, and a combination thereof, the fluoroelastomer product has reduced particle size compared to a second fluoroelastomer product having the same fluorine-containing elastomer composition as the fluoroelastomer product but without the microdiamond particles.

34. The method according to claim 33, wherein the curable fluorine-containing elastomer composition comprises at least one filler, and the method further comprises the step of adding the microdiamond particles to the fluorine-containing elastomer composition while adding the at least one filler to the at least one first curable fluoropolymer.

35. The method according to claim 33, further comprising the step of adding at least one curing agent before curing the curable fluorine-containing elastomer composition to form the fluoroelastomer product.

36. The method according to claim 33, wherein the at least one curable fluoropolymer is the at least one curable perfluoropolymer, the perfluorinated olefin monomer is tetrafluoroethylene, and the perfluoropolymer further comprises the perfluoroalkyl vinyl ether.

37. The method according to claim 33, wherein the compression set value of the fluoroelastomer product at 250°C / 70 hours / 25% deflection is reduced compared to the second fluoroelastomer product, and the curable fluorine-containing composition used to form the second fluoroelastomer product as needed further comprises a carbon black filler.

38. The method according to claim 37, wherein the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product further comprises a carbon black filler.

39. The method according to claim 38, wherein the fluoroelastomer product has reduced adhesion compared to the second fluoroelastomer product.

40. The method according to claim 33, wherein the fluoroelastomer product has improved resistance to fluorine-based plasma, oxygen-based plasma, hydrogen-based plasma, and combinations thereof compared to the second fluoroelastomer product.

41. The method according to claim 33, wherein the fluoroelastomer product has improved physical properties compared to the second fluoroelastomer product.

42. The method according to claim 33, wherein the compression set value of the fluoroelastomer product at 350°C / 70 hours / 18% deflection is reduced compared to the second fluoroelastomer product, and the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product as needed further comprises a carbon black filler.

43. A method for forming a fluoroelastomer product having reduced compression set, wherein the method is: A step of preparing a curable fluorine-containing elastomer composition comprising at least one first curable fluoropolymer, wherein the at least one first curable fluoropolymer is (i) at least one curable fluoropolymer comprising at least two fluorinated monomers, wherein (a) one of the at least two fluorinated monomers is a fluorinated olefin or a perfluoroalkyl vinyl ether, and (b) the other of the at least two fluorinated monomers is vinylidene fluoride or at least one fluorine-containing curable site monomer comprising at least one curable site, and (ii) (a) at least one curable perfluoropolymer comprising at least one perfluoro monomer selected from perfluoroolefin monomers and perfluoroalkyl vinyl ether monomers, and (b) at least one perfluorofluorine-containing curable site monomer comprising at least one curable site. The selected step from, The steps include adding microdiamond particles having an average particle size of more than 0.10 microns to 100 microns to the curable fluorine-containing elastomer composition, A method comprising the steps of curing the curable fluorine-containing elastomer composition to form the fluoroelastomer product, wherein the fluoroelastomer product is formed from the same curable fluorine-containing elastomer composition as the fluoroelastomer product, but has a reduced compression set value at 250°C / 70 hours / 25% deflection compared to a second fluoroelastomer product that does not contain microdiamond particles.

44. The method according to claim 43, wherein the at least one curable fluoropolymer is the at least one curable perfluoropolymer, the perfluorinated olefin monomer is tetrafluoroethylene, and the perfluoropolymer further comprises the perfluoroalkyl vinyl ether, and the method further comprises the step of adding at least one curing agent before, if necessary, curing the curable fluorine-containing elastomer composition to form the fluoroelastomer product.

45. The aforementioned fluoroelastomer product (i) When the fluoroelastomer product and the second fluoroelastomer product are exposed to a fluorine-based plasma, an oxygen-based plasma, a hydrogen-based plasma, or a combination thereof, the particulate matter is reduced compared to the second fluoroelastomer product; or (ii) Reduced adhesion compared to the second fluoroelastomer product; or (iii) Improved resistance to fluorine-based plasma, oxygen-based plasma, hydrogen-based plasma, and combinations thereof compared to the second fluoroelastomer product; or (iv) Improved physical properties compared to the second fluoroelastomer product The method according to claim 43, having the following characteristics.

46. The method according to claim 43, wherein the compression set value of the fluoroelastomer product at 350°C / 70 hours / 18% deflection is reduced compared to the second fluoroelastomer product.

47. The method according to claim 43 or 46, wherein the curable fluorine-containing elastomer composition used to form the second fluoroelastomer product further comprises a carbon black filler.

48. A method for forming a fluoroelastomer product having reduced adhesion, wherein the method is: A step of preparing a curable fluorine-containing elastomer composition comprising at least one first curable fluoropolymer, wherein the at least one first curable fluoropolymer is (i) at least one curable fluoropolymer comprising at least two fluorinated monomers, wherein (a) one of the at least two fluorinated monomers is a fluorinated olefin or a perfluoroalkyl vinyl ether, and (b) the other of the at least two fluorinated monomers is vinylidene fluoride or at least one fluorine-containing curable site monomer comprising at least one curable site, and (ii) (a) at least one curable perfluoropolymer comprising at least one perfluoro monomer selected from perfluoroolefin monomers and perfluoroalkyl vinyl ether monomers, and (b) at least one perfluorofluorine-containing curable site monomer comprising at least one curable site. The selected step from, The steps include adding microdiamond particles having an average particle size of more than 0.10 microns to 100 microns to the curable fluorine-containing elastomer composition, A method comprising the steps of curing the curable fluorine-containing elastomer composition to form the fluoroelastomer product, wherein the fluoroelastomer product is formed from the same curable fluorine-containing elastomer composition as the fluoroelastomer product, but has reduced adhesion compared to a second fluoroelastomer product that does not contain microdiamond particles.

49. A method for forming a fluoroelastomer product having reduced particulate matter, wherein the method is A step of preparing a curable fluorine-containing elastomer composition comprising at least one first curable fluoropolymer, wherein the at least one first curable fluoropolymer is (i) at least one curable fluoropolymer comprising at least two fluorinated monomers, wherein (a) one of the at least two fluorinated monomers is a fluorinated olefin or a perfluoroalkyl vinyl ether, and (b) the other of the at least two fluorinated monomers is vinylidene fluoride or at least one fluorine-containing curable site monomer comprising at least one curable site, and (ii) (a) at least one curable perfluoropolymer comprising at least one perfluoro monomer selected from perfluoroolefin monomers and perfluoroalkyl vinyl ether monomers, and (b) at least one perfluorofluorine-containing curable site monomer comprising at least one curable site. The selected step from, The steps include adding microdiamond particles having an average particle size of more than 0.10 microns to about 100 microns to the curable fluorine-containing elastomer composition, A method comprising the steps of curing the curable fluorine-containing elastomer composition to form the fluoroelastomer product, wherein the fluoroelastomer product is usable at a usage temperature of at least about 350°C.

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