Fluoropolymer, aqueous dispersion, composition and cross-linked product

Abstract

The present invention provides a fluorine-containing polymer comprising tetrafluoroethylene units (1) and a fluorine-containing polymer derived from the general formula (2): CF2=CF(CF2) n The monomer unit (2) of the perfluorodiene shown in CF=CF2 (where n represents an integer from 2 to 10) has a content of tetrafluoroethylene unit (1) of 98.0 mol% to 99.999 mol% or more relative to all monomer units constituting the fluoropolymer, and a content of monomer unit (2) of 0.001 mol% to 2.0 mol% relative to all monomer units constituting the fluoropolymer.

Description

Technical Field

[0001] This invention relates to fluoropolymers, aqueous dispersions, compositions, and crosslinkers. Background Technology

[0002] Patent document 1 describes a polytetrafluoroethylene molded body obtained by crosslinking crosslinked polytetrafluoroethylene having reactive functional groups such as cyano (-CN).

[0003] Patent document 2 describes a fluoropolymer, which is a copolymer of a perfluorodiene monomer of formula (1) and at least one other free radical polymerizable monomer, characterized in that all or at least one of the other free radical polymerizable monomers is a fluoropolymer.

[0004] CF2 = CFO(CF2CF(CF3)O) n (CF2) m Equation (1) is CF = CF²

[0005] (Where, n and m are each an independent integer from 1 to 3.)

[0006] Patent document 3 describes an elastomer composition for windshield wipers, characterized in that it is made by mixing 5 to 10 parts by weight of irradiated crosslinked PTFE (polytetrafluoroethylene) powder into 100 parts by weight of a base elastomer polymer.

[0007] Patent document 4 describes a sealing material composition which is made by mixing 5 to 50% by weight of fluorinated resin micro powders such as polytetrafluoroethylene powder into a fluorinated elastomer whose main components are repeating units derived from fluorinated olefins and perfluoroalkyl vinyl ethers, respectively.

[0008] Existing technical documents

[0009] Patent Literature

[0010] Patent Document 1: International Publication No. 2007 / 052664

[0011] Patent Document 2: Japanese Patent Application Publication No. 5-230151

[0012] Patent Document 3: Japanese Patent Application Publication No. 2001-151086

[0013] Patent Document 4: International Publication No. 97 / 08239 Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] The purpose of this invention is to provide a fluoropolymer that can be easily manufactured.

[0016] In addition, the present invention aims to provide a composition that can produce a crosslinked compound with excellent plasma resistance and low compression set.

[0017] Methods for solving problems

[0018] According to the present invention, a fluoropolymer is provided, comprising a tetrafluoroethylene unit (1) and a component from general formula (2):

[0019] CF2 = CF(CF2) n CF = CF2

[0020] (In the formula, n represents an integer from 2 to 10.) The content of the tetrafluoroethylene unit (1) of the monomer unit (2) of the perfluorodiene shown is 98.0 mol% to 99.999 mol% relative to all the monomer units constituting the fluoropolymer, and the content of the monomer unit (2) is 0.001 mol% to 2.0 mol% relative to all the monomer units constituting the fluoropolymer.

[0021] In the fluoropolymer of the present invention, the 1030-1040 cm⁻¹ value obtained by infrared absorption spectroscopy analysis of the above-mentioned fluoropolymer is... -1 The peak height (h1) at this location is relative to 2360–2370 cm. -1 The spectral intensity ratio (h1 / h0) of the peak height (h0) appearing at a given location is preferably 0.001 or higher.

[0022] In the fluoropolymer of the present invention, the infrared absorption spectrum analysis of the above-mentioned fluoropolymer yields a value of 1780–1800 cm⁻¹. -1 The peak height (h2) at this location is relative to 2360–2370 cm. -1 The spectral intensity ratio (h2 / h0) of the peak height (h0) appearing at a given location is preferably 0.20 or less.

[0023] The peak temperature of the fluoropolymer of the present invention is preferably above 300°C.

[0024] The preferred melt viscosity of the fluoropolymer of the present invention, measured at 380°C, is 1.0 × 10⁻⁶. 3 Mooring ~7.0×10 6 moor.

[0025] The fluoropolymer of the present invention is preferably in powder form.

[0026] In addition, according to the present invention, an aqueous dispersion is provided which contains the above-mentioned fluoropolymer.

[0027] In addition, according to the present invention, a composition is provided which contains the above-mentioned fluoropolymer (hereinafter sometimes referred to as fluoropolymer (P)) and a polymer (E) different from fluoropolymer (P).

[0028] In the compositions of the present invention, the polymer (E) is preferably a perfluoroelastomer.

[0029] In the composition of the present invention, the content of fluoropolymer (P) is preferably 0.5 to 100 parts by mass relative to 100 parts by mass of polymer (E).

[0030] The composition of the present invention preferably further contains at least one selected from the group consisting of inorganic nitrides, organotin compounds, ammonia-generating compounds and crosslinking agents.

[0031] In addition, according to the present invention, a crosslinking compound is provided, which is obtained from the above composition.

[0032] The effects of the invention

[0033] According to the present invention, a fluoropolymer that can be easily manufactured can be provided.

[0034] In addition, according to the present invention, a composition capable of obtaining a crosslinked compound with excellent plasma resistance and low compression set can be provided. Attached Figure Description

[0035] Figure 1 This is the infrared absorption spectrum of the fluoropolymer obtained in Synthesis Example 4. The horizontal axis represents the wavenumber (cm²). -1 The vertical axis represents absorbance (A) (%).

[0036] Figure 2 The infrared absorption spectra of the fluoropolymer obtained in Comparative Synthesis Example 1 are shown. Detailed Implementation

[0037] The specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments.

[0038] The fluoropolymer of the present invention contains tetrafluoroethylene (TFE) units (1) and monomer units (2).

[0039] In contrast, Patent Document 1 describes a method for obtaining a PTFE resin that is less prone to deformation compared to conventional PTFE resins by introducing reactive functional groups such as cyano (-CN) into polytetrafluoroethylene (PTFE) and crosslinking it. However, if reactive functional groups such as cyano are introduced into PTFE, these reactive functional groups are easily hydrolyzed, which can be expected to improve storage stability.

[0040] Furthermore, Patent Document 2 describes obtaining a copolymer by copolymerizing a perfluorodiene monomer having the structure of formula (1) described above. Such perfluorodiene monomers have the problem of high reactivity and difficulty in controlling the copolymerization reaction.

[0041] Patent document 3 describes that irradiated crosslinked PTFE obtained by irradiation with an electron beam exhibits more than 1000 times the wear resistance compared to uncrosslinked PTFE. However, if PTFE is irradiated with an electron beam, the PTFE decomposes during crosslinking, thus reducing its heat resistance. Furthermore, an apparatus for irradiating with an electron beam is required, making it difficult to reduce manufacturing costs.

[0042] The monomer unit (2) contained in the fluoropolymer of the present invention is obtained by using the general formula (2):

[0043] CF2 = CF(CF2) n CF = CF2

[0044] (Where, n represents an integer from 2 to 10.) The perfluorodiene shown is copolymerized with TFE, thereby being incorporated into the fluoropolymer. Since the copolymerization reaction of TFE and perfluorodiene is relatively easy to control, the fluoropolymer of the present invention can be easily manufactured. In addition, easily hydrolyzable reactive functional groups are not introduced into the fluoropolymer, so the fluoropolymer of the present invention also has excellent storage stability. Furthermore, since it is not modified by radiation irradiation, the fluoropolymer of the present invention exhibits excellent heat resistance and improved creep resistance compared with uncrosslinked PTFE. The fluoropolymer of the present invention may contain two or more monomer units from the perfluorodiene shown in general formula (2) as monomer units (2).

[0045] In general formula (2), n represents an integer from 2 to 10. n is preferably an integer from 3 to 9, more preferably an integer from 4 to 8. In addition, from the perspective of ease of synthesis of perfluorodiene, n is preferably 2, 4, 6, 8 or 10, more preferably 2, 4, 6 or 8, even more preferably 4, 6 or 8, and particularly preferably 4 or 8.

[0046] As the perfluorodiene represented by general formula (2), it is preferably selected from at least one of the group consisting of CF2=CF(CF2)2CF=CF2, CF2=CF(CF2)4CF=CF2, CF2=CF(CF2)6CF=CF2 and CF2=CF(CF2)8CF=CF2, and more preferably CF2=CF(CF2)4CF=CF2.

[0047] Because perfluorodienes do not contain CH bonds, it is possible to introduce the same structure as the TFE unit into the polymer chain through perfluorodiene polymerization. The excellent heat resistance of the fluoropolymers of this invention can also be explained for this reason.

[0048] The content of TFE units in the fluoropolymer is 98.0 mol% to 99.999 mol% relative to all monomer units constituting the fluoropolymer. Since it can improve heat resistance while maintaining excellent storage stability and creep resistance, the content of TFE units is preferably 98.5 mol% or more, more preferably 98.8 mol% or more, preferably 99.995 mol% or less, and more preferably 99.990 mol% or less.

[0049] The content of monomer unit (2) in the fluoropolymer is 0.001 mol% to 2.0 mol% relative to all monomer units constituting the fluoropolymer. Since it can improve storage stability and creep resistance while maintaining excellent heat resistance, the content of monomer unit (2) is preferably 0.002 mol% or more, more preferably 0.005 mol% or more, even more preferably 0.010 mol% or more, preferably 1.5 mol% or less, more preferably 1.2 mol% or less, even more preferably 1.0 mol% or less, and particularly preferably 0.80 mol% or less.

[0050] The content of monomer units in fluoropolymers can be calculated by appropriately combining NMR and FT-IR according to the types of monomers.

[0051] The fluoropolymers of the present invention may contain monomer units derived from monomers other than TFE and perfluorodiene.

[0052] As for other monomers, there are no particular limitations as long as they can copolymerize with TFE and perfluorodienes. Examples include perfluoroolefins such as hexafluoropropylene [HFP]; chlorofluoroolefins such as trifluorochloroethylene [CTFE]; hydrofluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF]; fluoroalkyl vinyl ethers; fluoroalkyl allyl ethers; perfluoroalkyl ethylene; ethylene, etc.

[0053] When performing infrared absorption spectroscopy analysis on the fluoropolymers of the present invention, it is preferable that the infrared absorption spectrum obtained is in the range of 1030 to 1040 cm⁻¹. -1 Characteristic peaks are observed at 1030–1040 cm⁻¹. These peaks were obtained through infrared absorption spectroscopy analysis of fluoropolymers. -1 The peak height (h1) at this location is relative to 2360–2370 cm. -1 The spectral intensity ratio (h1 / h0) of the peak height (h0) appearing at the peak is preferably 0.001 or more, more preferably 0.005 or more, preferably 2.500 or less, more preferably 1.500 or less, further preferably 1.000 or less, and particularly preferably 0.650 or less.

[0054] Estimated height: 1030–1040 cm -1The absorption peaks appearing at [value] are from the C-C bonds of the branched portion of the polymer chain formed by copolymerization of perfluorodiene. It is speculated that the magnitude of the spectral intensity ratio (h1 / h0) represents the amount of structure from the branched portion of the perfluorodiene introduced into the polymer chain. It is speculated that if perfluorodiene is polymerized, the same structure as the TFE unit is introduced into the polymer chain, but the fluoropolymer containing monomer units from perfluorodiene exhibits a higher absorption peak at 1030–1040 cm⁻¹. -1 The presence of characteristic peaks in the vicinity does not correspond to those observed in existing PTFE. Therefore, the fluoropolymer of this invention has a significantly different structure from conventional PTFE. Fluoropolymers containing monomer units derived from perfluorodienes and exhibiting these characteristic peaks demonstrate excellent storage stability, heat resistance, and creep resistance.

[0055] When performing infrared absorption spectroscopy analysis on the fluoropolymers of the present invention, it is preferable that the infrared absorption spectrum obtained is in the range of 1780–1800 cm⁻¹. -1 No obvious peaks were observed at 1780–1800 cm⁻¹. Infrared absorption spectroscopy analysis of fluoropolymers yielded peaks in the 1780–1800 cm⁻¹ range. -1 The peak height (h2) at this location is relative to 2360–2370 cm. -1 The spectral intensity ratio (h2 / h0) of the peak height (h0) appearing at a given location is preferably 0.25 or less, more preferably 0.20 or less, and more preferably 0.15 or more.

[0056] Hypothesis: The magnitude of the spectral intensity ratio (h2 / h0) indicates not only the amount of CF bonds in the fluoropolymer chain but also the amount of double bonds present in the side chains of the fluoropolymer. When the fluoropolymer has double bonds in its side chains, this is particularly evident in the infrared absorption spectrum at 1780–1800 cm⁻¹. -1 Strong absorption was observed at [location]. Fluoropolymers with small spectral intensity ratios (h2 / h0) have no or almost no double bonds in their side chains, and therefore do not react with other polymers, for example, even when used in combination with them, and can persist in the composition with extreme stability.

[0057] From the perspective of heat resistance, the peak temperature of the fluoropolymer is preferably above 300°C, more preferably above 310°C, even more preferably above 320°C, preferably below 347°C, and more preferably below 345°C.

[0058] Fluoropolymers preferably have a high peak temperature. The peak temperature of a fluoropolymer is preferably 333°C or higher, more preferably 335°C or higher, more preferably 347°C or lower, more preferably 345°C or lower. Fluoropolymers with high peak temperatures tend to exhibit fibrillation properties and non-melt processability.

[0059] Fluoropolymers also preferably have a low peak temperature. The peak temperature of the fluoropolymer is preferably 322°C or higher, more preferably 324°C or higher, more preferably 333°C or lower, and more preferably 332°C or lower. Fluoropolymers with lower peak temperatures tend to exhibit non-fibrillatory properties and tend to exhibit melt processability.

[0060] Regarding the peak temperature, approximately 10 mg of the fluoropolymer powder that has not been heated to temperatures above 300°C is accurately weighed, placed in a dedicated aluminum pan, and measured using a TG / DTA (Differential Thermogravimetric Analysis) device. The peak temperature is determined by heating the fluoropolymer powder without raising it above 300°C using a TG / DTA device at a rate of 10°C / min, and can be specified as the temperature corresponding to the maximum value appearing in the resulting differential thermal analysis (DTA) curve.

[0061] From the perspective of heat resistance, the 1.0% weight loss temperature of the fluoropolymer is preferably 400°C or higher, more preferably 405°C or higher, and even more preferably 410°C or higher. The upper limit of the 1.0% weight loss temperature can be 500°C.

[0062] Regarding the 1.0% mass weight loss temperature, approximately 10 mg of fluoropolymer powder that has not been heated to temperatures above 300°C is accurately weighed, placed in a dedicated aluminum pan, and measured using a TG / DTA (Differential Thermogravimetric Analysis) device. The 1.0% mass weight loss temperature can be specified by heating the aluminum pan at a rate of 10°C / min under atmospheric conditions within a temperature range of 25°C to 600°C.

[0063] The specific gravity of the fluoropolymer is preferably 2.130 to 2.230, more preferably 2.130 to 2.190.

[0064] Specific gravity can be determined by either the SSG method or the water displacement method. The SSG method uses a sample molded according to ASTM D4895-89 and is determined by the water displacement method according to ASTM D 792.

[0065] One embodiment of the fluoropolymer has fibrillability. The fibrillable fluoropolymer can be molded using its fibrillability via paste extrusion molding. Furthermore, the fluoropolymer can be extruded via paste extrusion molding, and the extrudate can be calendered into sheets or stretched into porous bodies.

[0066] One embodiment of the fluoropolymer does not exhibit fibrillation properties. Fluoropolymers that do not exhibit fibrillation properties have excellent chemical stability, extremely low surface energy, and are not prone to forming fibrils. Therefore, they are suitable as additives for improving lubricity, coating surface texture, etc., in the manufacture of plastics, inks, cosmetics, coatings, greases, office automation equipment parts, colorants, etc. (see, for example, Japanese Patent Application Publication No. 10-147617).

[0067] The presence or absence of fibrillability can be determined using "paste extrusion," a representative method for molding powders made from TFE polymers, i.e., "high molecular weight PTFE powder." This is because, typically, high molecular weight PTFE exhibits fibrillability when paste extrusion is possible. If the unfired molded article obtained by paste extrusion does not possess substantial strength or elongation—for example, if the elongation is 0% and it breaks upon stretching—it can be considered to lack fibrillability.

[0068] One embodiment of the fluoropolymer has non-melt processability. Fluoropolymers with non-melt processability tend to exhibit fibrillation.

[0069] One embodiment of the fluoropolymer does not have non-melt processability. Fluoropolymers that do not have non-melt processability tend to be less prone to forming fibrils. By using a fluoropolymer that does not have non-melt processability (a fluoropolymer that has melt processability) in the composition of the present invention described later, it is possible to improve the plasma resistance (especially the durability against NF3 remote plasma) of the crosslinked product obtained from the composition.

[0070] Non-melt processability refers to the property that the melt flow rate cannot be determined according to ASTM D1238 and D2116 at temperatures higher than the aforementioned peak temperatures.

[0071] The melt viscosity of the fluoropolymer in one embodiment, measured at 380°C, is 1.0 × 10⁻⁶. 3 Mooring ~7.0×10 6 The preferred value is 1.0 × 10⁻⁶. 4 Mooring~5.0×10 6 Po, further preferably 1.0 × 10 5 ~2.0×10 6 Po. By using a fluoropolymer with a melt viscosity within the above range in the compositions of the present invention described later, the plasma resistance (especially the durability against NF3 remote plasma) of the crosslinked products obtained from the compositions can be significantly improved.

[0072] The peak temperature, fibrillability, and non-melt processability of fluoropolymers can be adjusted by modifying the polymerization conditions of the fluorinated monomers used to manufacture the fluoropolymers. For example, to increase the molecular weight of the obtained fluoropolymer, appropriately selecting the polymerization conditions of the fluorinated monomers can increase the peak temperature of the fluoropolymer or produce a fluoropolymer with fibrillability and non-melt processability. Conversely, during the polymerization of fluorinated monomers, by using chain transfer agents and appropriately selecting the type and amount of chain transfer agents, the peak temperature of the fluoropolymer can be reduced, or a fluoropolymer without fibrillability and non-melt processability can be produced.

[0073] The fluoropolymers of the present invention can be manufactured by polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. A method for manufacturing fluoropolymers by emulsion polymerization will be described.

[0074] The fluoropolymers of the present invention can be manufactured, for example, by polymerizing TFE and perfluorodiene in the presence of an aqueous medium, a polymerization initiator, and a surfactant. More specifically, TFE and perfluorodiene, an aqueous medium, a surfactant, and other additives as needed are added to a reactor, the contents of the reactor are stirred, and the reactor is then maintained at a predetermined polymerization temperature. A predetermined amount of polymerization initiator is then added to initiate the polymerization reaction, thereby enabling the polymerization of TFE and perfluorodiene. After the polymerization reaction begins, TFE, perfluorodiene, a polymerization initiator, a chain transfer agent, etc., may be added as needed.

[0075] Aqueous media refers to the reaction medium in which polymerization takes place, which is a liquid containing water. There are no particular limitations as long as the aqueous medium contains water; it can contain water and non-fluorinated organic solvents such as alcohols, ethers, and ketones, and / or fluorinated organic solvents with a boiling point below 40°C.

[0076] As a polymerization initiator, there are no particular limitations as long as free radicals can be generated within the polymerization temperature range; known oil-soluble and / or water-soluble polymerization initiators can be used. Furthermore, it can be combined with reducing agents to initiate polymerization in a redox manner.

[0077] The amount of polymerization initiator added relative to the aqueous medium is preferably 1 ppm or more, more preferably 5 ppm or more, more preferably 5000 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 ppm or less.

[0078] As polymerization initiators, water-soluble free radical polymerization initiators are preferred, such as ammonium salts, potassium salts, and sodium salts of persulfate, perboric acid, perchloric acid, perphosphoric acid, and percarbonate, organic peroxides such as disuccinic acid peroxide and diglutaric acid peroxide, tert-butyl maleate peroxide, and tert-butyl hydroperoxide.

[0079] Examples of surfactants include fluorinated surfactants. For example, fluorinated surfactants are...

[0080] General formula: X-(CF2) m1 -COOX

[0081] (In the formula, X represents H or F, m1 represents an integer from 3 to 5, and X represents H, NH4, or an alkali metal atom.) The fluorine-containing compounds shown...

[0082] General formula: CF3OCF(CF3)CF2OCF(CF3)COOX

[0083] (In the formula, X represents H, NH4 or an alkali metal atom.) This refers to fluorine-containing compounds, etc.

[0084] The amount of surfactant added is preferably 10 ppm to 10% by mass relative to the aqueous medium.

[0085] Chain transfer agents can be used during polymerization. Examples of chain transfer agents include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, and dimethyl succinate, as well as isopentane, methane, ethane, propane, methanol, isopropanol, acetone, various thiols, carbon tetrachloride and other halogenated hydrocarbons, cyclohexane, etc.

[0086] Additives such as buffers, pH adjusters, stabilizers, and dispersants can be used during polymerization.

[0087] Preferred stabilizing agents include paraffin wax, fluorinated oils, fluorinated solvents, and silicone oils. One stabilizing agent can be used alone or in combination of two or more. Paraffin wax is more preferred. Paraffin wax can be liquid, semi-solid, or solid at room temperature, but is preferably a saturated hydrocarbon with 12 or more carbon atoms. The melting point of paraffin wax is typically preferred to be 40°C to 65°C, more preferably 50°C to 65°C.

[0088] The amount of stabilizing agent used relative to the aqueous medium is preferably 0.1% to 12% by mass.

[0089] Polymerization can be carried out under normal pressure and temperature. Typically, the polymerization temperature is 5℃ to 120℃, and the polymerization pressure is 0.05 MPaG to 10 MPaG. The polymerization temperature and pressure are appropriately determined based on the type of monomer, the molecular weight of the target fluoropolymer, the reaction rate, and other factors.

[0090] An aqueous dispersion containing a fluoropolymer is obtained by polymerizing TFE and perfluorodiene in an aqueous medium. The content of the fluoropolymer in the polymerized aqueous dispersion is typically 8% to 50% by mass relative to the aqueous dispersion.

[0091] Fluoropolymers can be recovered by coagulating them in an aqueous dispersion. There are no particular limitations on the method used to coagulate the fluoropolymers. For example, vigorous stirring of the aqueous dispersion can cause coagulation. Alternatively, water-soluble organic compounds such as methanol and acetone, inorganic salts such as potassium nitrate and ammonium carbonate, and inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid can be added as precipitants to the aqueous dispersion, followed by stirring to coagulate the fluoropolymers. After coagulation, the coagulated fluoropolymers can be recovered as a wetted polymer.

[0092] The obtained wet polymer can also be dried. The drying temperature is preferably 10°C to 300°C, more preferably 100°C to 300°C. By thoroughly drying it, a fluoropolymer powder can be obtained. The fluoropolymer of the present invention can be an aqueous dispersion of fluoropolymer particles in an aqueous medium, or it can be a fluoropolymer powder.

[0093] The fluoropolymers of the present invention (hereinafter sometimes referred to as fluoropolymers (P)) can be used for a variety of applications.

[0094] The fluoropolymers of this invention are easy to manufacture and exhibit excellent storage stability, heat resistance, and creep resistance, making them suitable for use in a variety of molded articles. In particular, the fluoropolymers of this invention are suitable for use in a variety of molded articles when they possess fibrillable properties or non-melt processability.

[0095] The molding method for obtaining fluoropolymers can be a conventional method, such as compression molding, plunger extrusion molding, paste extrusion molding, and other known methods.

[0096] Specific examples of molded articles include gaskets, liners, tubes, linings, coatings, insulating tapes, bearings, roofing membranes for inflatable tents, gas / liquid separation membranes, separators, and load membranes, among many other applications. The shape of the molded body is not particularly limited; examples include tubes, membranes, sheets, fibers, and porous membranes.

[0097] Furthermore, the fluoropolymers of the present invention are easy to manufacture and exhibit excellent storage stability, heat resistance, and creep resistance, thus making them suitable for use as fillers, for example. The fluoropolymers of the present invention are obtained by polymerizing perfluorodienes, but the double bonds present in perfluorodienes are eliminated through polymerization; therefore, the fluoropolymers of the present invention have little or no double bonds. Thus, the fluoropolymers of the present invention function as fillers but not as crosslinking agents.

[0098] Furthermore, the fluoropolymers of the present invention can also be used as additives. In particular, the fluoropolymers of the present invention are suitable for use as additives when they lack fibrillability or non-melt processability.

[0099] The fluoropolymers of this invention are suitable for use as molding materials, inks, cosmetics, coatings, lubricants, components for office automation equipment, additives for modifying colorants, and additives in plating solutions. Examples of molding materials include engineering plastics such as polyoxybenzoyl polyester, polyimide, polyamide, polyamide-imide, polyacetal, polycarbonate, and polyphenylene sulfide.

[0100] The fluoropolymers of the present invention, as additives for molding materials, are suitable for applications such as improving the non-adhesive and sliding properties of copier rollers, improving the texture of engineering plastic molded products such as furniture surface sheets, automotive dashboards, and appliance covers, improving the sliding properties and wear resistance of mechanical parts that generate mechanical friction, such as light-load bearings, gears, cams, push-button telephone buttons, projector and camera parts, and sliding materials, and as processing aids for engineering plastics.

[0101] The fluoropolymer of this invention can be used as an additive in coatings to improve the slip properties of varnishes and paints. The fluoropolymer of this invention can also be used as an additive in cosmetics to improve the slip properties of foundations and other cosmetic products.

[0102] The fluoropolymers of the present invention are also suitable for applications that improve the oil and water resistance of waxes, etc., and for applications that improve the lubricity of greases or colorants.

[0103] The fluoropolymer of the present invention can also be used as an electrode binder for secondary batteries or fuel cells, a hardness modifier for electrode binders, a waterproofing agent for electrode surfaces, etc.

[0104] The present invention also relates to a composition comprising a fluoropolymer (P) and a polymer (E) different from the fluoropolymer (P). The fluoropolymer (P) contained in the composition of the present invention is not only easy to manufacture, but also exhibits excellent storage stability, heat resistance, and creep resistance. Therefore, in addition to being able to be manufactured at low cost, the composition of the present invention can also yield crosslinked products with excellent plasma resistance and low compression set even after use under harsh conditions.

[0105] Examples of polymers (E) include resins and elastomers.

[0106] Examples of resins include fluoropolymers, polyamide resins, polyolefin resins, vinyl chloride resins, polyurethane resins, polyester resins, polyaramid resins, polyimide resins, polyamide-imide resins, polyphenylene ether resins, polyacetal resins, polycarbonate resins, acrylic resins, styrene resins, acrylonitrile / butadiene / styrene resins (ABS), cellulose resins, polyetheretherketone resins (PEEK), polysulfone resins, polyethersulfone resins (PES), polyetherimide resins, resins composed of ethylene / vinyl alcohol copolymers, polyphenylene sulfide resins, polybutylene naphthalate resins, polybutylene terephthalate resins, and polyphthalamide (PPA).

[0107] Examples of fluoropolymers include TFE / perfluoro(alkyl vinyl ether) copolymer [PFA], TFE / hexafluoropropylene copolymer [FEP], ethylene / TFE copolymer [ETFE], ethylene / TFE / hexafluoropropylene copolymer, polychlorotrifluoroethylene, chlorotrifluoroethylene / TFE copolymer, ethylene / chlorotrifluoroethylene copolymer, polyvinylidene fluoride [PVdF], TFE / vinylidene fluoride copolymer, and polyvinylidene fluoride.

[0108] As the polymer (E), an elastomer is preferred. Examples of elastomers include acrylonitrile-butadiene rubber (NBR) or its hydrogenated form (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural rubber (NR), isoprene rubber (IR), and other diene-based rubbers; ethylene-propylene-terpolymer rubber; silicone rubber; butyl rubber; epichlorohydrin rubber; acrylic rubber; chlorinated polyethylene (CPE); polymeric mixtures of nitrile rubber and vinyl chloride (PVC-NBR); ethylene propylene diene monomer (EPDM); chlorosulfonated polyethylene (CSM); and fluorinated elastomers.

[0109] As the polymer (E), a fluorinated elastomer is preferred. The fluorinated elastomer can be a partially fluorinated elastomer or a perfluorinated elastomer, but due to its excellent chemical resistance and heat resistance, and to maximize the synergistic effect brought about by its combination with the fluorinated polymer (P), a perfluorinated elastomer is preferred.

[0110] In this invention, a partially fluorinated elastomer refers to a fluorinated polymer containing fluorinated monomer units, wherein the content of perfluorinated monomer units relative to all monomer units is less than 90 mol%, and which is a fluorinated polymer having a glass transition temperature below 20°C and a melting peak (ΔH) size below 4.5 J / g.

[0111] In this invention, a perfluorinated elastomer refers to a fluoropolymer in which the content of perfluorinated monomer units relative to all monomer units is 90 mol% or more; it is a fluoropolymer with a glass transition temperature below 20°C and a melting peak (ΔH) size below 4.5 J / g; and further, it is a polymer in which the concentration of fluorine atoms contained in the fluoropolymer is 71% by mass or more. In this invention, the concentration of fluorine atoms contained in the fluoropolymer is calculated by considering the types and contents of each monomer constituting the fluoropolymer, and thus determining the concentration (by mass%) of fluorine atoms contained in the fluoropolymer.

[0112] In this invention, a perfluorinated monomer refers to a monomer whose molecule does not contain carbon-hydrogen bonds. The perfluorinated monomer can be a monomer in which several fluorine atoms bonded to carbon atoms are replaced by chlorine atoms, in addition to carbon and fluorine atoms; it can also be a monomer in which nitrogen, oxygen, and sulfur atoms are present in addition to carbon atoms. Preferably, the perfluorinated monomer is one in which all hydrogen atoms are replaced by fluorine atoms. The perfluorinated monomer does not contain monomers that provide crosslinking sites.

[0113] Examples of partially fluorinated elastomers include vinylidene fluoride (VdF) fluororubbers, tetrafluoroethylene (TFE) / propylene (Pr) fluororubbers, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) fluororubbers, ethylene / hexafluoropropylene (HFP) fluororubbers, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) fluororubbers, and ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) fluororubbers. Preferably, at least one type is selected from the group consisting of vinylidene fluoride fluororubbers and tetrafluoroethylene / propylene fluororubbers.

[0114] The aforementioned vinylidene fluoride-based fluororubber is preferably a copolymer composed of 45 mol% to 85 mol% of vinylidene fluoride and 55 mol% to 15 mol% of at least one other monomer capable of copolymerizing with vinylidene fluoride. More preferably, it is a copolymer composed of 50 mol% to 80 mol% of vinylidene fluoride and 50 mol% to 20 mol% of at least one other monomer capable of copolymerizing with vinylidene fluoride.

[0115] In this invention, the content of each monomer constituting the fluorinated elastomer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescence X-ray analysis according to the types of monomers.

[0116] Examples of other monomers capable of copolymerizing with vinylidene fluoride include TFE, HFP, fluoroalkyl vinyl ethers, chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutylene, hexafluoroisobutylene, fluoroethylene, and general formula (11): CHX 11 =CX 11 Rf 11 (In the formula, there are two X's)11 One is H, the other is F, Rf 11 It is a fluorinated monomer represented by a straight-chain or branched fluoroalkyl group having 1 to 12 carbon atoms, with the general formula (12): CH2=CH-(CF2). n -X 12 (where X) 12 Fluorinated monomers (where H or F, n is an integer from 3 to 10); monomers providing crosslinking sites; and non-fluorinated monomers such as ethylene, propylene, and alkyl vinyl ethers. These can be used individually or in any combination. Preferably, at least one monomer selected from the group consisting of TFE, HFP, fluoroalkyl vinyl ethers, and CTFE is used.

[0117] As the above-mentioned fluoroalkyl vinyl ether, the preferred option is...

[0118] General formula (13): CF2 = CF - ORf 13

[0119] (where Rf) 13 This refers to perfluoroalkyl groups having 1 to 8 carbon atoms. (The fluorinated monomers shown are...)

[0120] General formula (14): CF2=CFOCF2ORf 14

[0121] (where Rf) 14 It includes straight-chain or branched perfluoroalkyl groups with 1 to 6 carbon atoms, cyclic perfluoroalkyl groups with 5 to 6 carbon atoms, and straight-chain or branched perfluorooxyalkyl groups with 2 to 6 carbon atoms containing 1 to 3 oxygen atoms. (The fluorinated monomers shown are...)

[0122] General formula (15): CF2=CFO(CF2CF(Y 15 )O) m (CF2) n F

[0123] (where Y) 15 Represents a fluorine atom or a trifluoromethyl group. m is an integer from 1 to 4. n is an integer from 1 to 4. ) is at least one of the fluorine-containing monomers in the group consisting of the fluorine-containing monomers shown, more preferably the fluorine-containing monomers shown in general formula (13).

[0124] Specific examples of vinylidene fluoride-based fluororubbers include VdF / HFP rubber, VdF / HFP / TFE rubber, VdF / CTFE rubber, VdF / CTFE / TFE rubber, VdF / fluorinated monomer rubber of general formula (11), VdF / fluorinated monomer / TFE rubber of general formula (11), VdF / perfluoro(methyl vinyl ether) [PMVE] rubber, VdF / PMVE / TFE rubber, and VdF / PMVE / TFE / HFP rubber. Among the VdF / fluorinated monomer rubbers of general formula (11), VdF / CH2=CFCF3 rubber is preferred, and among the VdF / fluorinated monomer / TFE rubbers of general formula (11), VdF / TFE / CH2=CFCF3 rubber is preferred.

[0125] The VdF / CH2=CFCF3 rubber described above is preferably a copolymer composed of 40 mol% to 99.5 mol% VdF and 0.5 mol% to 60 mol% CH2=CFCF3, more preferably a copolymer composed of 50 mol% to 85 mol% VdF and 15 mol% to 50 mol% CH2=CFCF3.

[0126] The aforementioned tetrafluoroethylene / propylene fluororubber is preferably a copolymer composed of 45 mol% to 70 mol% tetrafluoroethylene, 55 mol% to 30 mol% propylene, and 0 to 5 mol% fluorinated monomers providing crosslinking sites.

[0127] The aforementioned fluorinated elastomer may be a perfluorinated elastomer. Preferably, the perfluorinated elastomer is selected from at least one of the following groups: a perfluorinated elastomer containing a TFE unit, such as a TFE / fluorinated monomer copolymer of general formula (13), (14) or (15), and a TFE / fluorinated monomer / monomer copolymer of general formula (13), (14) or (15) that provides a crosslinking site.

[0128] In the case of TFE / PMVE copolymer, its composition is preferably 45-90 / 10-55 (mol%), more preferably 55-80 / 20-45, and even more preferably 55-70 / 30-45.

[0129] In the case of a TFE / PMVE monomer copolymer providing crosslinking sites, the preferred composition is 45–89.9 / 10–54.9 / 0.01–4 (mol%), more preferably 55–77.9 / 20–49.9 / 0.1–3.5, and even more preferably 55–69.8 / 30–44.8 / 0.2–3.

[0130] In the case of TFE / fluorinated monomer copolymers of general formulas (13), (14) or (15) with 4 to 12 carbon atoms, it is preferably 50 to 90 / 10 to 50 (mol%), more preferably 60 to 88 / 12 to 40, and even more preferably 65 to 85 / 15 to 35.

[0131] In the case of a TFE / fluorinated monomer / monomer copolymer of general formula (13), (14) or (15) having 4 to 12 carbon atoms, the preferred ratio is 50 to 89.9 / 10 to 49.9 / 0.01 to 4 (mol%), more preferably 60 to 87.9 / 12 to 39.9 / 0.1 to 3.5, and even more preferably 65 to 84.8 / 15 to 34.8 / 0.2 to 3.

[0132] If it falls outside this composition range, it loses its properties as a rubber elastomer and tends to exhibit properties closer to those of a resin.

[0133] As the above-mentioned perfluorinated elastomer, it is preferably selected from at least one of the following groups: a fluorinated monomer copolymer of TFE / general formula (15) / monomer copolymer providing crosslinking site, a fluorinated monomer copolymer of TFE / general formula (15), a fluorinated monomer copolymer of TFE / general formula (13), and a fluorinated monomer copolymer of TFE / general formula (13) / monomer copolymer providing crosslinking site.

[0134] Other examples of perfluorinated elastomers mentioned above include those described in International Publication No. 97 / 24381, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, and Japanese Patent Publication No. 5-13961.

[0135] The monomer that provides the crosslinking site refers to a monomer with a crosslinking group (sulfurization point monomer), which provides the crosslinking site to the fluorinated elastomer for crosslinking by a crosslinking agent.

[0136] Examples of monomers that provide cross-linking sites include

[0137] General formula (16): CX 4 2 = CX 5 R f 2 X 6

[0138] (where X) 4 X 5 Each is independently H, F, or an alkyl group having 1 to 5 carbon atoms, R f 2It can be a straight-chain or branched alkylene or oxidized alkylene that can have one or more ether-bonded oxygen atoms, can have an aromatic ring, and whose hydrogen atoms can be partially or completely replaced by fluorine atoms. 6 The monomer can be an iodine atom, bromine atom, nitrile group, carboxyl group, alkoxycarbonyl group, hydroxyl group, vinyl group, azide group, sulfonyl azide group, carbonyl azide group, or alkynyl group. The alkynyl group can be ethynyl.

[0139] The monomer providing the crosslinking site is preferably at least one selected from the group consisting of:

[0140] General formula (17): CX 16 2 = CX 16 -Rf 16 CHR 16 X 17

[0141] (where X) 16 Each can be independently a hydrogen atom, a fluorine atom, or CH3, Rf 16 It is a fluorinated alkylene, a perfluoroalkylene, a fluorinated (poly)oxyalkylene, or a perfluoro (poly)oxyalkylene, R 16 For hydrogen atoms or CH3, X 17 Fluorine-containing monomers (represented by iodine or bromine atoms)

[0142] General formula (18): CX 16 2 = CX 16 -Rf 17 X 17

[0143] (where X) 16 Each can be independently a hydrogen atom, a fluorine atom, or CH3, Rf 17 It is a fluorinated alkylene, a perfluoroalkylene, a fluorinated (poly)oxyalkylene, or a perfluoro (poly)oxyalkylene, X 17 Fluorine-containing monomers (represented by iodine or bromine atoms)

[0144] General formula (19): CF2 = CFO(CF2CF(CF3)O) m (CF2) n -X 18

[0145] (In the formula, m is an integer from 0 to 5, n is an integer from 1 to 3, X) 18 Fluorine-containing monomers represented by cyano, azide, sulfonyl azide, carbonyl azide, carboxyl, alkoxy carbonyl, alkynyl, iodine atom, bromine atom, or -CH2I)

[0146] General formula (20): CH2=CFCF2O(CF(CF3)CF2O)m (CF(CF3)) n -X 19

[0147] (In the formula, m is an integer from 0 to 5, n is an integer from 1 to 3, X) 19 Fluorine-containing monomers represented by cyano, carboxyl, alkoxycarbonyl, iodine, bromine or -CH2OH, and

[0148] General formula (21): CR 20 2 = CR 20 -Z-CR 20 =CR 20 2

[0149] (where R is in the formula) 20 Each is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z is a straight-chain or branched alkylene group having 1 to 18 carbon atoms, with or without oxygen atoms, a cycloalkylene group having 3 to 18 carbon atoms, an alkylene group or alkylene oxide having 1 to 10 carbon atoms that is at least partially fluorinated, or...

[0150] -(Q) p -CF₂O-(CF₂CF₂O) m (CF2O) n -CF2-(Q) p -

[0151] (In the formula, Q is alkylene or alkylene oxide. p is 0 or 1. m / n is 0.2 to 5.) This represents a (per)fluoropolyalkylene oxide with a molecular weight of 500 to 10000. The monomer is shown in the formula.

[0152] X 16 Preferably, it contains fluorine atoms. Rf 16 and Rf 17 Preferably, it is a perfluoroalkylene group having 1 to 5 carbon atoms. 16 Preferably, it contains hydrogen atoms. X 18 Preferably, it is a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2I. X 19 Preferably, it is a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2OH.

[0153] The monomers providing the crosslinking sites are preferably selected from CF2=CFOCF2CF(CF3)OCF2CF2CN, CF2=CFOCF2CF(CF3)OCF2CF2COOH, CF2=CFOCF2CF(CF3)OCF2CF2CH2I, CF2=CFOCF2CF2CH2I, CH2=CFCF2OCF(CF3)CF2OCF(CF3)CN, and CH2=CFCF2OCF(CF3)CF2OCF(CF3)CN. At least one of the following groups: )COOH, CH2=CFCF2OCF(CF3)CF2OCF(CF3)CH2OH, CH2=CHCF2CF2I, CH2=CH(CF2)2CH=CH2, CH2=CH(CF2)6CH=CH2 and CF2=CFO(CF2)5CN, more preferably at least one of the following groups: CF2=CFOCF2CF(CF3)OCF2CF2CN and CF2=CFOCF2CF2CH2I.

[0154] From the perspective of excellent compression set characteristics at high temperatures, the glass transition temperature of the above-mentioned fluorinated elastomer is preferably -70°C or higher, more preferably -60°C or higher, and even more preferably -50°C or higher. Furthermore, from the perspective of good cold resistance, it is preferably 5°C or lower, more preferably 0°C or lower, and even more preferably -3°C or lower.

[0155] The glass transition temperature mentioned above can be determined as follows: Using a differential scanning calorimeter (manufactured by Mettler Toredo, DSC822e), a 10 mg sample is heated at 10 °C / min to obtain a DSC curve. The temperature of the midpoint between the extension of the baseline representing the second-order phase transition of the DSC curve and the tangent at the inflection point of the DSC curve is determined and taken as the glass transition temperature mentioned above.

[0156] From the perspective of good heat resistance, the Mooney viscosity ML(1+20) of the above-mentioned fluorinated elastomer at 170°C is preferably 30 or more, more preferably 40 or more, and even more preferably 50 or more. Furthermore, from the perspective of good processability, it is preferably 150 or less, more preferably 120 or less, and even more preferably 110 or less.

[0157] From the perspective of good heat resistance, the Mooney viscosity ML(1+20) of the above-mentioned fluorinated elastomer at 140°C is preferably 30 or more, more preferably 40 or more, and even more preferably 50 or more. Furthermore, from the perspective of good processability, it is preferably 180 or less, more preferably 150 or less, and even more preferably 110 or less.

[0158] From the perspective of good heat resistance, the Mooney viscosity ML(1+10) of the above-mentioned fluorinated elastomer at 100°C is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more. Furthermore, from the perspective of good processability, it is preferably 120 or less, more preferably 100 or less, and even more preferably 80 or less.

[0159] The Mooney viscosity described above can be measured using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES at 170°C, 140°C, or 100°C according to JIS K6300.

[0160] The aforementioned partially fluorinated elastomers and perfluorinated elastomers can be manufactured using conventional methods. Iodine or bromine compounds can be used as chain transfer agents because they offer advantages such as a narrow molecular weight distribution, easy molecular weight control, and the ability to introduce iodine or bromine atoms at the ends. Examples of polymerization methods using iodine or bromine compounds include emulsion polymerization (iodine transfer polymerization) carried out under pressure in an aqueous medium in a substantially anaerobic environment in the presence of iodine or bromine compounds. Representative examples of the iodine or bromine compounds used include, for example, those with the general formula:

[0161] R 21 I x Br y

[0162] (In the formula, x and y are integers from 0 to 2 and satisfy 1≤x+y≤2, R) 21 It is a compound consisting of saturated or unsaturated fluorocarbon or chlorofluorocarbon groups with 1 to 16 carbon atoms, or a hydrocarbon group with 1 to 3 carbon atoms, and may contain oxygen atoms. By using iodine or bromine compounds, iodine or bromine atoms are introduced into the polymer to function as crosslinking points.

[0163] Examples of iodine and bromine compounds include, for instance, 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, CF₂Br₂, BrCF₂CF₂Br, CF₃CFBrCF₂Br, and CFClBr₂. BrCF2CFClBr, CFBrClCFClBr, BrCF2CF2CF2Br, BrCF2CFBrOCF3, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluoro-1-butene, 2-bromo-4-iodoperfluoro-1-butene, monoiodomonobromo-substituted derivatives of benzene, diiodomonobromo-substituted derivatives, and (2-iodoethyl) and (2-bromoethyl)-substituted derivatives, etc. These compounds can be used alone or in combination with each other.

[0164] Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are preferred in terms of polymerization reactivity, crosslinking reactivity, and ease of acquisition.

[0165] The fluorinated elastomers described above preferably have cyano (-CN) groups. In fluorinated elastomers with cyano (-CN) groups, the cyano groups can be crosslinked by cyclizing trimerization to form triazine rings, which can impart excellent compression set properties and heat resistance to the crosslinked products.

[0166] As the above-mentioned fluorinated elastomer with cyano groups, it is preferable to have cyano groups (-CN groups) at the end of the main chain and / or on the side chains.

[0167] Examples of fluorinated elastomers that have cyano (-CN) groups at the end of the main chain and / or on the side chains include perfluorinated elastomers and partially fluorinated elastomers.

[0168] As a perfluorinated elastomer having cyano (-CN) groups at the end of the main chain and / or on the side chains, examples include copolymers of TFE / fluorinated monomers / monomers providing crosslinking sites shown in general formulas (13), (14), or (15) where the monomer providing the crosslinking site is a monomer with a cyano (-CN) group. In this case, from the perspective of good crosslinking properties and heat resistance, the content of the monomer unit with a cyano (-CN) group relative to the total amount of TFE unit and fluorinated monomer units shown in general formulas (13), (14), and (15) can be 0.1 mol% to 5 mol%, or 0.3 mol% to 3 mol%. More suitable compositions are as described above.

[0169] In addition, examples of monomers containing a cyano group (-CN group) include:

[0170] Formula: CY 1 2 = CY 1 (CF2) n -CN

[0171] (where Y) 1 Each atom is independently either a hydrogen atom or a fluorine atom, where n is an integer from 1 to 8.

[0172] Formula: CF2=CFCF2Rf 8 -CN

[0173] (where Rf) 8 For -(OCF2) n -or-(OCF(CF3)) n - (n is an integer from 0 to 5)

[0174] Formula: CF2=CFCF2(OCF(CF3)CF2) m (OCH2CF2CF2) n OCH2CF2-CN

[0175] (In the formula, m is an integer from 0 to 5, and n is an integer from 0 to 5)

[0176] Equation: CF2=CFCF2(OCH2CF2CF2) m (OCF(CF3)CF2) n OCF(CF3)-CN

[0177] (In the formula, m is an integer from 0 to 5, and n is an integer from 0 to 5)

[0178] Formula: CF2=CF(OCF2CF(CF3)) m O(CF2) n -CN

[0179] (In the formula, m is an integer from 0 to 5, and n is an integer from 1 to 8)

[0180] Formula: CF2=CF(OCF2CF(CF3)) m -CN

[0181] (In the formula, m is an integer from 1 to 5)

[0182] Formula: CF2=CFOCF2(CF(CF3)OCF2) n CF(-CN)CF3

[0183] (In the formula, n is an integer from 1 to 4)

[0184] Formula: CF2 = CFO(CF2) n OCF(CF3)-CN

[0185] (In the formula, n is an integer from 2 to 5)

[0186] Formula: CF2 = CFO(CF2) n -(C6H4)-CN

[0187] (In the formula, n is an integer from 1 to 6)

[0188] Formula: CF2=CF(OCF2CF(CF3)) n OCF2CF(CF3)-CN

[0189] (In the formula, n is an integer from 1 to 2)

[0190] Formula: CH2=CFCF2O(CF(CF3)CF2O) n CF(CF3)-CN

[0191] (In the formula, n is an integer from 0 to 5)

[0192] Formula: CF2 = CFO(CF2CF(CF3)O) m (CF2) n -CN

[0193] (In the formula, m is an integer from 0 to 5, and n is an integer from 1 to 3)

[0194] Formula: CH2=CFCF2OCF(CF3)OCF(CF3)-CN

[0195] Formula: CH2=CFCF2OCH2CF2-CN

[0196] Formula: CF2 = CFO(CF2CF(CF3)O) m CF2CF(CF3)-CN

[0197] (In the formula, m is an integer greater than or equal to 0)

[0198] Formula: CF2=CFOCF(CF3)CF2O(CF2) n -CN

[0199] (In the formula, n is an integer greater than or equal to 1)

[0200] Formula: CF2=CFOCF2OCF2CF(CF3)OCF2-CN

[0201] The monomers shown can be used individually or in any combination.

[0202] Of the above, the preferred option is...

[0203] Formula: CF2=CF(OCF2CF(CF3)) m O(CF2) n -CN

[0204] (where m is an integer from 0 to 5 and n is an integer from 1 to 8) The monomer shown is more preferably CF2=CFOCF2CF(CF3)OCF2CF2CN.

[0205] These perfluorinated elastomers can be manufactured using conventional methods.

[0206] Specific examples of this perfluoroelastomer include fluororubber as described in International Publication No. 97 / 24381, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, and Japanese Patent Publication No. 5-13961.

[0207] Examples of partially fluorinated elastomers having cyano (-CN) groups at the end of the main chain and / or on the side chains include vinylidene fluoride (VdF) fluororubbers, tetrafluoroethylene (TFE) / propylene fluororubbers, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) fluororubbers, ethylene / hexafluoroethylene (HFP) fluororubbers, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) fluororubbers, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) fluororubbers, fluorosilicone fluororubbers, or fluorophosphazene fluororubbers. They can be used individually or in any combination without impairing the effects of the present invention.

[0208] Vinylidene fluoride-based fluororubber refers to a fluorinated copolymer composed of 45 mol% to 85 mol% of vinylidene fluoride and 55 mol% to 15 mol% of at least one other monomer capable of copolymerizing with vinylidene fluoride. Preferably, it refers to a fluorinated copolymer composed of 50 mol% to 80 mol% of vinylidene fluoride and 50 mol% to 20 mol% of at least one other monomer capable of copolymerizing with vinylidene fluoride.

[0209] Examples of other monomers capable of copolymerizing with vinylidene fluoride include fluorinated monomers such as TFE, CTFE, trifluoroethylene, HFP, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutylene, perfluoro(alkyl vinyl ether) (PAVE), and fluorinated vinylidene, as well as non-fluorinated monomers such as ethylene, propylene, and alkyl vinyl ethers. These can be used individually or in any combination. Among these, TFE, HFP, and perfluoro(alkyl vinyl ether) are preferred.

[0210] Specific examples of rubbers include VdF-HFP series rubbers, VdF-HFP-TFE series rubbers, VdF-CTFE series rubbers, and VdF-CTFE-TFE series rubbers.

[0211] These partially fluorinated elastomers can be manufactured using conventional methods.

[0212] In addition, thermoplastic fluororubber composed of elastomeric fluoropolymer segments and non-elastomeric fluoropolymer segments can be used as fluoropolymers.

[0213] Relative to 100 parts by weight of polymer (E), the content of fluoropolymer (P) in the composition of the present invention is preferably 0.5 parts by weight to 100 parts by weight, more preferably 5 parts by weight to 50 parts by weight, and even more preferably 10 parts by weight to 40 parts by weight. Furthermore, when polymer (E) is a fluoroelastomer, relative to 100 parts by weight of the fluoroelastomer, the content of fluoropolymer (P) in the composition of the present invention is preferably 0.5 parts by weight to 100 parts by weight, more preferably 5 parts by weight to 50 parts by weight, and even more preferably 10 parts by weight to 40 parts by weight.

[0214] <Other ingredients>

[0215] The compositions of the present invention may further contain fillers (except for fluoropolymers (P)).

[0216] Examples of fillers include imide-based fillers with imide structures such as polyimide, polyamide-imide, and polyether-imide; organic fillers made of engineering plastics such as polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyether ether ketone, polyether ketone, and polyoxybenzoic acid ester; metal oxide fillers such as silicon oxide, alumina, and yttrium oxide; metal carbides such as silicon carbide and aluminum carbide; metal nitride fillers such as silicon nitride and aluminum nitride; and inorganic fillers such as carbon black, aluminum fluoride, and fluorinated carbon.

[0217] Among them, from the perspective of the shielding effect of various plasmas, carbon black, alumina, silicon oxide, yttrium oxide, silicon carbide, silicon nitride, polyimide, and fluorinated carbon are preferred.

[0218] In addition, the aforementioned inorganic and organic fillers can be used alone or in combination of two or more.

[0219] The filler content is preferably 0.01 to 100 parts by weight relative to 100 parts by weight of polymer (E), more preferably 0.05 to 50 parts by weight, further preferably 0.05 to 10 parts by weight, and particularly preferably 0.05 to 3 parts by weight.

[0220] Especially in fields where high purity and non-polluting properties are not required, common additives such as processing aids, plasticizers, and colorants can be mixed into the composition as needed, or one or more commonly used crosslinking agents or crosslinking aids that are different from the above can be mixed in.

[0221] The above composition may also contain an organic basic compound. Examples of organic basic compounds include...

[0222] Formula: CH3(CH2) 17 -NH2-octadecylamine;

[0223] Formula: H2N-C(O)-(CH2) 11 -CH=CH-(CH2)7CH3 erucamide;

[0224] Oleamide with the formula: H2N-C(O)-(CH2)7-CH=CH-(CH2)7CH3;

[0225] Formula: 1,6-hexanediamine of H2N-(CH2)6-NH2

[0226] Mode:

[0227] [Chemistry 1]

[0228] 1,8-diazabicycloundec-7-ene (DBU), etc.

[0229] The compositions of the present invention preferably further contain at least one selected from the group consisting of inorganic nitrides, organotin compounds, ammonia-generating compounds, and crosslinking agents. These are particularly preferred when the polymer (E) is an elastomer. By including these components such as crosslinking agents in the compositions of the present invention, crosslinked products can be readily obtained from the compositions of the present invention. Hereinafter, a preferred configuration of the composition when the polymer (E) is a fluorinated elastomer will be described.

[0230] There are no particular limitations on inorganic nitrides, and examples include silicon nitride (Si3N4), lithium nitride, titanium nitride, aluminum nitride, boron nitride, vanadium nitride, and zirconium nitride. Among these, silicon nitride is preferred because it can supply nanoscale particles.

[0231] Examples of organotin compounds include tetraphenyltin and triphenyltin.

[0232] As a compound that generates ammonia, it is preferred to be a compound that generates ammonia at temperatures between 40°C and 330°C.

[0233] Urea or its derivatives, or ammonium salts, are preferred as ammonia-producing compounds; urea or ammonium salts are more preferred; and urea is even more preferred. The ammonium salt can be an organic or inorganic ammonium salt. Alternatively, the ammonia-producing compound can be a compound that reacts with trace amounts of water to produce ammonia.

[0234] Examples of urea derivatives include biuret, thiourea, urea hydrochloride, and biuret.

[0235] Examples of organic ammonium salts include compounds described in Japanese Patent Application Publication No. 9-111081, International Publication No. 00 / 09603, and International Publication No. 98 / 23675, such as ammonium salts of polyfluorocarboxylic acids like ammonium perfluorohexanoate and ammonium perfluorooctanoate; ammonium salts of polyfluorosulfonic acids like ammonium perfluorohexanesulfonate and ammonium perfluorooctanesulfonate; ammonium salts of phosphoric acids or phosphonic acids containing polyfluoroalkyl groups like ammonium perfluorohexanephosphate and ammonium perfluorooctanephosphate; and ammonium salts of non-fluorinated carboxylic acids or sulfonic acids like ammonium benzoate, ammonium adipate, and ammonium phthalate.

[0236] Examples of inorganic ammonium salts include compounds described in Japanese Patent Application Publication No. 9-111081, such as ammonium sulfate, ammonium carbonate, ammonium nitrate, and ammonium phosphate.

[0237] In addition, examples of ammonia-producing compounds include acetaldehyde, hexamethylenetetramine, formamidin, formamidin hydrochloride, formamidin acetate, tert-butyl carbamate, benzyl carbamate, HCF2CF2CH(CH3)OCONH2, and phthalamide.

[0238] Examples of crosslinking agents include those used in peroxide crosslinking, polyol crosslinking, polyamine crosslinking, triazine crosslinking, oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking. When the fluorinated elastomer is a fluorinated elastomer having a cyano (-CN) group, the crosslinking agent is preferably at least one selected from the group consisting of oxazole crosslinking agents, imidazole crosslinking agents, and thiazole crosslinking agents.

[0239] The crosslinking agent used in peroxide crosslinking can be any organic peroxide that can readily generate peroxide free radicals in the presence of heat or a redox system. Specifically, examples include 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-tert-butylperoxide (PerbutylD), tert-butylcumyl peroxide (PerbutylC), dicumyl peroxide (Percumyl D, Percumyl D-40, Percumyl D-40MB(T)), α,α-bis(tert-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (Perhexa 25B, Perhexa 25B-40), and 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (Perhexyne 25B, Perhexyne...). 25B-40), benzoyl peroxide, tert-butyl peroxide, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane (Perhexa 25Z), tert-butyl maleate peroxide (t-butyl MA), tert-butyl isopropyl carbonate peroxide (Perbutyl I-75), methyl ethyl ketone peroxide (Permek D(DR), Permek H(HR, HY), Permek N(NR, NY), Permek S(SR), Permek F(FR), Permek G(GR, GY)), cyclohexanone peroxide (Perhexa H), acetylacetone peroxide (Percure AH, AL), 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane (Perhexa TMH), 1,1-di(tert-hexylperoxy)cyclohexane (Perhexa HC), 1,1-di(tert-butylperoxy)-2-methylcyclohexane (Perhexa MC), 1,1-di(tert-butylperoxy)cyclohexane (Perhexa C-80(S), Perhexa C-75(EB), Perhexa C(C), Perhexa C-40, Perhexa C-40MB(S)), 2,2-di(tert-butylperoxy)butane (Perhexa 22), 4,4-di(tert-butylperoxy)valerate (Perhexa V, Perhexa V-40(F)), 2,2-di(4,4-di(tert-butylperoxy)cyclohexyl)propane (Pertetra A), terpene hydroperoxide (Permenta H), dicumyl hydroperoxide (Percumyl P), 1,1,3,3-Tetramethylbutyl hydroperoxide (Perocta H), cumene hydroperoxide (Percumyl H-80), tert-butyl hydroperoxide (Perbutyl H-69), di(2-tert-butylisopropyl peroxide)benzene (Perbutyl P, Perbutyl P-40, Peroximon F-40, Perbutyl P-40MB(K)), ditert-hexyl peroxide (Perhexyl D), diisobutyryl peroxide (Peroyl IB), di(3,5,5-trimethylhexanoyl) peroxide (Peroyl 355(S)), dilauryl peroxide (Peroyl L), succinyl peroxide (Peroyl SA), di(3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, and mixtures of benzoyl peroxide (NYPER BMT-K40, NYPER BMT-M), benzoyl peroxide (NYPER BW, NYPER BO, NYPER FF, NYPER BS, NYPER E, NYPER NS), bis(4-methylbenzoyl) peroxide (NYPER PMB), di-n-propyl peroxide (Peroyl NPP-50M), diisopropyl peroxide (Peroyl IPP-50, Peroyl IPP-27), di(4-tert-butylcyclohexyl) peroxide (Peroyl TCP), di(2-ethylhexyl) peroxide (Peroyl OPP), di-sec-butyl peroxide (Peroyl SBP), cumyl peroxide neodecanoate (Percumyl ND, Percumyl ND-50E), 1,1,3,3-tetramethylbutyl peroxide neodecanoate (Perocta ND, Perocta ND-50E), tert-hexyl peroxide neodecanoate (Perhexyl ND, Perhexyl ND-50E), tert-butyl peroxide neodecanoate (Perbutyl ND, Perbutyl ND-50E), tert-butyl peroxyn-2-hydroxyl peroxide (Perbutyl NHP), tert-hexyl peroxyn-2-hydroxyl peroxide (Perhexyl PV, Perhexyl PV-50E), tert-butyl peroxyn-2-hydroxyl peroxide (Perbutyl PV, Perbutyl PV-40E), 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate (Perocta O), 2,5-dimethyl-2,5-Di(2-ethylhexanoyl)peroxyhexane (Perhexa 25O), tert-hexyl peroxy(2-ethylhexanoate) (PerhexylO, Percure HO(N)), tert-butyl peroxy(2-ethylhexanoate) (Perbutyl O, Percure O), tert-hexyl peroxyisopropyl monocarbonate (Perhexyl I), tert-butyl peroxy-3,5,5-trimethylhexanoate (Perbutyl 355), tert-butyl peroxylaurate (Perbutyl L), tert-butyl peroxy-2-ethylhexyl monocarbonate (Perbutyl E), tert-hexyl peroxybenzoate (Perhexyl Z), tert-butyl peroxyacetate (Perbutyl A), a mixture of tert-butyl peroxy-3-methylbenzoate and tert-butyl peroxybenzoate (Perbutyl ZT), tert-butyl peroxybenzoate (Perbutyl Z), tert-butyl peroxyallyl monocarbonate (Peromer) Organic peroxides such as AC, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone (BTTB-25), and 2,3-dimethyl-2,3-diphenylbutane (NOFMER BC-90) are preferred. Dialkyl-type substances are preferred. Furthermore, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane is particularly preferred. The type and amount of organic peroxide are typically selected considering factors such as the amount of active -OO- and decomposition temperature.

[0240] Furthermore, any compound that is reactive against peroxide free radicals and polymer free radicals can be used as a crosslinking aid at this time. Examples include multifunctional compounds with functional groups such as -CH=CH2, -CH2CH=CH2, -CF=CF2, -C(CF3)=CF2, -C(CH3)=CF2, -CF=CF(CF3), -CF=CF(CH3), -C(C6H5)=CF2, -CF=CF(C6H5), -CH=CF2, -CF=CHF, -C(CF3)=CHF, -CF=CH(CF3), and -CH=CF(CF3) (in each formula, "C6H5" represents phenyl). Specifically, examples include triallyl cyanurate, triallyl isocyanurate (TAIC), 1,3,5-triacryloylhexahydro-1,3,5-triazine, triallyl trimellitate, N,N'-n-phenylene bismaleimide, diacetylacetate terephthalate, diallyl phthalate, tetraallyl terephthalamide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris(2,3,3-trifluoro-2-propenyl)-1,3,5-triazine-2,4,6-trione), tris(diallylamine)-triazine, triallyl phosphite, N,N-diallylacrylamide, and 1,6-divinyldodecylfluorohexane.

[0241] In addition, as a crosslinking aid used with peroxide crosslinking agents, general formula (31) can also be cited:

[0242] [Chemistry 2]

[0243]

[0244] (In the formula, there are 6 R's) 31 Each is independently H, a halogen atom, or an optional halogenated group having 1 to 5 carbon atoms that may be inserted with an ether bond; Z 31 It is a compound, optionally containing heteroatoms, linear or branched, having 1 to 18 carbon atoms, and optionally halogenated alkylene, cycloalkylene, or (per)fluoropolyalkylene oxide.

[0245] Examples of compounds represented by general formula (31) include compounds represented by general formula (32), compounds represented by general formula (33), compounds represented by general formula (34), etc.

[0246] General formula (32):

[0247] [Chemistry 3]

[0248]

[0249] (In the formula, j is an integer from 2 to 10, preferably an integer from 4 to 8, and 4 R...) 32 Each is independently H, F, or an alkyl or (per)fluoroalkyl group having 1 to 5 carbon atoms.

[0250] General formula (33):

[0251] [Chemistry 4]

[0252]

[0253] (where Y) 31 Each is independently F, Cl, or H, Y 32 Each can be independently F, Cl, H, or OR. 33 (Here, R) 33 (These are branched or straight-chain alkyl groups that can be substantially or completely fluorinated or chlorinated), Z 33 It can be an optional fluorinated divalent group with 2 to 10 carbon atoms that can be inserted with an ether bond, preferably Z. 33 -(CF2) is an integer where m is between 3 and 5. m -Base, the compound represented by general formula (33) is preferably F2C=CF-O-(CF2)5-O-CF=CF2.

[0254] General formula (34):

[0255] [Chemistry 5]

[0256]

[0257] (where Y) 31 Y 32 and Z 33 As mentioned above, R 34 Each is independently H, F, or an alkyl or (per)fluoroalkyl group having 1 to 5 carbon atoms.

[0258] Examples of crosslinking aids used in conjunction with crosslinking agents or peroxide crosslinking agents include those having at least one general formula (35):

[0259] [Chemistry 6]

[0260]

[0261] (where R is in the formula) 35 ~R 37 Each is independently a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, or a substituted or unsubstituted aryl group, R 35 ~R 37 At least one of them is a fluorine atom or a group containing a fluorine atom. m is an integer from 1 to 5. When m is 2 or more, there are m R atoms. 35 ~R 37 These can be the same or different. Compounds with the structure shown (with or without substituents on the hydrogen atoms of the benzene ring). When m is 1, it is preferable to have two or more of these structures.

[0262] Examples of compounds having the structure shown in general formula (36) include compounds shown in general formula (36), compounds shown in general formula (37), etc.

[0263] General formula (36):

[0264] [Chemistry 7]

[0265]

[0266] (where R is in the formula) 35 ~R 37 As mentioned above. p is an integer from 0 to 2, and n is an integer from 2 to 6.

[0267] General formula (37):

[0268] [Chemistry 8]

[0269]

[0270] (where R is in the formula) 35 ~R 37 As described above. R38 It can be a single bond, -SO2-, -O-, -S-, -CO-, a heteroatom-containing group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group. m is an integer from 1 to 5. These groups may be partially or completely fluorinated.

[0271] As a group containing heteroatoms, there are no particular limitations as long as it is a divalent group containing heteroatoms. Examples of heteroatoms include oxygen, nitrogen, sulfur, boron, and phosphorus atoms.

[0272] Examples of crosslinking agents used in polyol crosslinking include bisphenol A and bisphenol AF.

[0273] Examples of crosslinking agents used in polyamine crosslinking include 1,6-hexanediamine carbamate, N,N'-dicinnamyl-1,6-hexanediamine, and 4,4'-bis(aminocyclohexyl)methane carbamate.

[0274] Examples of crosslinking agents used in oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking include, for example, the bis(diaminophenyl) crosslinking agent shown in general formula (41), the diaminophenol crosslinking agent, the bis(aminophenylthiophenol) crosslinking agent, the bis(aminohydrazone) crosslinking agent shown in general formula (42), the aminohydrazone crosslinking agent shown in general formula (43), or the bis(amide oxime) crosslinking agent shown in general formula (44), and the compound shown in general formula (45).

[0275] General formula (41):

[0276] [Chemistry 9]

[0277]

[0278] (where R is in the formula) 41 It is -SO2-, -O-, -CO-, alkylene groups with 1 to 6 carbon atoms, perfluoroalkylene groups with 1 to 10 carbon atoms, or a single bond, or

[0279] [Chemistry 10]

[0280]

[0281] The group shown, R 42 and R 43 One is -NH2 and the other is -NHR 44 -NH2, -OH or -SH, R 44 It is a hydrogen atom, a fluorine atom, or a monovalent organic group, preferably R. 42 -NH2, R 43 -NHR 44Preferred examples of alkylene groups having 1 to 6 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, and hexylene. Examples of perfluoroalkylene groups having 1 to 10 carbon atoms include...

[0282] [Chemistry 11]

[0283]

[0284] It should be noted that these compounds are known as examples of bis(diaminophenyl) compounds in Japanese Patent Application Publication No. 2-59177, Japanese Patent Application Publication No. 8-120146, etc.

[0285] General formula (42):

[0286] [Chemistry 12]

[0287]

[0288] (R 41 As mentioned above, R 45 Each can be independently any one of the following groups.

[0289] [Chemistry 13]

[0290]

[0291] General formula (43):

[0292] [Chemistry 14]

[0293]

[0294] (where Rf) 41 It is a perfluoroalkylene group with 1 to 10 carbon atoms.

[0295] General formula (44):

[0296] [Chemistry 15]

[0297]

[0298] (In the formula, n is an integer from 1 to 10.)

[0299] General formula (45): HN = CR 45 R 46

[0300] (where R is in the formula) 45 Choose freely from H, NH2 and NHR 47 In the group formed, R 46 Choose freely Ph, SO2H, NR 48 R 49In the group consisting of 2-pyridine and CH2CONH2, R 47 R is selected from the group consisting of Ph, NH2, and CN. 48 Selected from the group consisting of H, NHPh, CH2CONH2, straight-chain alkyl groups with 1 to 8 carbon atoms, and branched-chain alkyl groups with 1 to 8 carbon atoms, and R 49 Choose from Ph, COOC(CH3)3, NH2, CH2COOH, CSNH2, and CNHNH3. + Cl - p-Phenyl CN,

[0301] [Chemistry 16]

[0302]

[0303] In the group consisting of COPh.

[0304] These diaminophenol-based crosslinking agents, diaminobenzylthiophenol-based crosslinking agents, or diaminophenyl-based crosslinking agents have previously been used in crosslinking systems with cyano groups as crosslinking points. However, they react with both carboxyl and alkoxycarbonyl groups to form oxazole, thiazole, and imidazole rings, providing crosslinks.

[0305] In addition, general formula (46) can also be cited as a crosslinking agent: X 41 -(CH2) n -R 50 -(CH2) m -X 41 (where X) 41 Each can be independently alkynyl, nitrile, or Y-. 41 P N3(Y 41 For SO, SO2, C6H4, or CO, p is 0 or 1), n ​​and m are independent integers from 1 to 4, R 50 Choose Freedom

[0306] i) Fluoroalkylene groups having 3 to 10 carbon atoms,

[0307] ii) Fluoroalkoxides with 3 to 10 carbon atoms,

[0308] iii) Replacing aryl groups,

[0309] iv) Oligomers containing copolymer units of vinylidene fluoride and perfluorinated (methyl vinyl ether),

[0310] v) Oligomers containing copolymer units of vinylidene fluoride and hexafluoropropylene,

[0311] vi) Oligomers containing copolymer units of tetrafluoroethylene and perfluoro(methyl vinyl ether) and

[0312] vii) The crosslinking agent shown in the group consisting of oligomers comprising copolymer units of tetrafluoroethylene and hydrocarbon olefins. This crosslinking agent is preferably used with a fluorinated elastomer having a nitrile, azide, sulfonyl azide, carbonyl azide, or alkynyl group. For example, the nitrile group of the fluorinated elastomer reacts with the azide group of the crosslinking agent to form a tetrazolium ring, providing the crosslinked product.

[0313] As particularly preferred crosslinking agents, examples include compounds having two or more 3-amino-4-hydroxyphenyl or 3-amino-4-mercaptophenyl groups, or those of general formula (47):

[0314] [Chemistry 17]

[0315]

[0316] (where R is in the formula) 41 R 42 and R 43 The compounds shown above, specifically, for example, are 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (common name: bis(aminophenol)AF), 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane, tetraaminobenzene, bis-3,4-diaminophenylmethane, bis-3,4-diaminophenyl ether, 2,2-bis(3,4-diaminophenyl)hexafluoropropane, 2,2-bis[3-amino-4-(N-phenylamino)] [Phenylene]hexafluoropropane, 2,2-bis[3-amino-4-(N-methylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-ethylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-propylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-perfluorophenylamino)phenyl]hexafluoropropane, 2,2-bis[3-amino-4-(N-benzylamino)phenyl]hexafluoropropane, etc.

[0317] Among these, 2,2-bis[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane is preferred as a crosslinking agent in terms of heat resistance, steam resistance, amine resistance, and good crosslinking properties.

[0318] The content of at least one of the following, selected from the group consisting of inorganic nitrides, organotin compounds, ammonia-generating compounds and crosslinking agents, is preferably 0.05 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the fluorinated elastomer.

[0319] The above composition can be prepared by mixing the components using conventional polymer processing machinery, such as open mills, Banbury mixers, kneaders, etc. Alternatively, it can be prepared using a closed mixer. The above composition is suitable for use as a molding material for crosslinking molding to obtain crosslinked products.

[0320] Alternatively, a composition containing a fluoropolymer (P) and a fluoroelastomer can be prepared by co-precipitating the fluoropolymer (P) and the fluoroelastomer in an aqueous medium, and other components can be added to the composition as desired.

[0321] The crosslinked compound of the present invention is obtained from the above composition. The crosslinked compound of the present invention exhibits excellent plasma resistance and low compression set even under harsh conditions. From the viewpoint of further superior plasma resistance and compression set characteristics, the crosslinked compound of the present invention is preferably a crosslinked compound obtained by crosslinking the above composition.

[0322] One method for obtaining a crosslinked product from the composition is to crosslink the preform obtained by using the composition as a molding material. The method for obtaining a preform by using the composition as a molding material can be a conventional method, such as heating and compressing using a mold, pressing into a heated mold, or extruding using an extruder. In the case of extruded products such as hoses or wires, a crosslinked product can be obtained by heating and crosslinking based on steam or the like after extrusion.

[0323] The crosslinking described above can be carried out in the order of primary crosslinking and secondary crosslinking. Primary crosslinking is preferably performed at 150°C to 200°C for 5 to 120 minutes, more preferably at 170°C to 190°C for 5 to 60 minutes. Known crosslinking methods can be used, such as pressure crosslinking.

[0324] The secondary crosslinking is preferably performed at 180°C to 320°C for 2 to 24 hours, and more preferably at 200°C to 310°C for 5 to 20 hours. Alternatively, temperature variations within this temperature range are also permissible. Known crosslinking methods can be used as the crosslinking method, such as heat crosslinking.

[0325] The crosslinked material of the present invention can be suitably used as a sealing material for semiconductor manufacturing apparatuses that require particularly high heat resistance, especially for semiconductor manufacturing apparatuses subjected to high-density plasma irradiation. Examples of such sealing materials include O-rings, square rings, gaskets, sealing pads, oil seals, bearing seals, and lip seals.

[0326] In addition, it can be used in various polymer products used in semiconductor manufacturing equipment, such as diaphragms, tubes, hoses, various rubber rollers, belts, etc. It can also be used as a coating material and a lining material.

[0327] It should be noted that the semiconductor manufacturing apparatus described in this invention is not particularly limited to apparatus for manufacturing semiconductors, but broadly includes all manufacturing apparatuses used in the semiconductor field that require high cleanliness, such as apparatuses for manufacturing liquid crystal panels or plasma panels, for example, the following apparatuses.

[0328] (1) Etching apparatus

[0329] Dry etching apparatus

[0330] Plasma etching device

[0331] Reactive ion etching device

[0332] Reactive ion beam etching apparatus

[0333] sputtering etching equipment

[0334] Ion beam etching equipment

[0335] wet etching apparatus

[0336] Ashing device

[0337] (2) Cleaning device

[0338] Dry etching cleaning equipment

[0339] UV / O3 cleaning device

[0340] Ion beam cleaning device

[0341] Laser beam cleaning device

[0342] Plasma cleaning device

[0343] Gas Etching Cleaning Equipment

[0344] Extraction and cleaning device

[0345] Soxhlet extraction and cleaning apparatus

[0346] High-temperature and high-pressure extraction and cleaning device

[0347] Microwave extraction and cleaning device

[0348] Supercritical extraction and cleaning device

[0349] (3) Exposure device

[0350] photolithography machine

[0351] Coating machine and developing machine

[0352] (4) Grinding device

[0353] CMP device

[0354] (5) Film forming device

[0355] CVD equipment

[0356] Sputtering device

[0357] (6) Diffusion-ion implantation device

[0358] Oxidation diffusion device

[0359] Ion implantation device

[0360] The crosslinked material of the present invention can exhibit excellent performance as a sealing material for, for example, CVD equipment, plasma etching equipment, reactive ion etching equipment, ashing equipment or excimer laser exposure machine.

[0361] The embodiments have been described above, but it is understood that various changes can be made to the methods and details without departing from the spirit and scope of the claims.

[0362] Example

[0363] Next, embodiments will be given to illustrate the implementation of the present invention, but the present invention is not limited to the embodiments described.

[0364] The values ​​in the examples were measured using the following methods.

[0365] <Solid component concentration>

[0366] 1g of aqueous dispersion was dried in a blower dryer at 150°C for 60 minutes. The mass of the heating residue was expressed as a percentage relative to the mass of the aqueous dispersion (1g).

[0367] <Average primary particle size>

[0368] The average primary particle size was calculated as follows: After determining the correlation between the transmittance of 550 nm light incident on a specified cell containing an aqueous dispersion of fluoropolymer with a solid content adjusted to 0.15% by mass and the number-average primary particle size calculated by measuring the orientation diameter using a transmission electron microscope, the transmittance measured on the obtained sample was applied to the above correlation to calculate the average primary particle size (calibration curve method).

[0369] <Infrared Absorption Spectroscopy Analysis>

[0370] Infrared absorption spectroscopy analysis was performed using a Fourier transform infrared spectroscopy analyzer to obtain the infrared absorption spectrum of the fluoropolymer powder obtained through precipitation and drying. The height ratio of each peak appearing in the obtained absorption spectrum was calculated using the following method.

[0371] Spectral intensity ratio 1 = h1 / h0

[0372] Spectral intensity ratio 2 = h2 / h0

[0373] h0: Harmonics of CF (2360~2370cm) -1 peak height

[0374] h1: Stretching vibration of the branch (1030~1040cm) -1 peak height

[0375] h2: C = C's stretching (1780~1800cm) -1 peak height

[0376] <Content of perfluorinated diene units>

[0377] pass 19 The determination was performed using F-NMR analysis.

[0378] Peak temperature

[0379] Approximately 10 mg of fluoropolymer powder, which has not been heated to temperatures above 300°C, was accurately weighed and placed in a dedicated aluminum pan. The powder was then measured using a TG / DTA (Differential Thermal and Thermogravimetric Analysis) device. Regarding the peak temperature, the aluminum pan was heated at a rate of 10°C / minute within an atmospheric temperature range from 25°C to 600°C to obtain a differential thermal analysis (DTA) curve. The temperature corresponding to the maximum value on the obtained DTA curve was taken as the peak temperature.

[0380] <Deformation rate>

[0381] 1.7 g of PTFE powder was filled into a cylindrical mold with a diameter of 13 mm at room temperature. Then, pressure was slowly applied and maintained at 29.4 MPa for 5 minutes before being removed from the mold to obtain a preform. The preform was placed in an air-circulating furnace at 40 °C and heated to 370 °C at a heating rate of 25 °C / hour. It was then sintered at 370 °C for 90 minutes and cooled to 40 °C at a cooling rate of 25 °C / hour before being removed from the furnace and slowly cooled to room temperature. Cylindrical compression test pieces with a diameter of 13.0 mm and a height of 5.85 mm were cut from the obtained preform.

[0382] The obtained test specimens and compression fixtures were preheated to 200°C. The specimens were then compressed to a compression ratio of 30% at 200°C (compressing a 5.85 mm height specimen to a 4.095 mm height). After compression at 200°C for 24 hours, the test specimens were removed from the compression fixtures and allowed to stand at 23°C for 30 minutes. The height of the specimen (t1) was measured. The deformation rate was calculated using the following formula. A smaller deformation rate indicates better creep resistance.

[0383] Deformation rate (%) = (t0-t1) / t0 × 100

[0384] t0: Height of the test piece before the test (mm)

[0385] t1: Height of the test piece after the compression test (mm)

[0386] In the above experiment, t0 = 5.85 mm.

[0387] Melt viscosity

[0388] According to ASTM D 1238, using a flow testing apparatus (manufactured by Shimadzu Corporation) and a 2Φ-8L mold, a 2g sample preheated at 380°C for 5 minutes was held at the aforementioned temperature under a load of 0.7MPa for measurement. The fluoropolymers obtained in Synthetic Examples 1-4 did not melt, therefore melt viscosity could not be measured.

[0389] Standard Specific Gravity (SSG)

[0390] The determination was performed using samples molded according to ASTM D 4895-89 by the water displacement method according to ASTM D 792.

[0391] Synthesis Example 1 (Preparation of Fluoropolymers)

[0392] 150 g of deionized water, 6 g of paraffin wax, and 0.225 g of ammonium 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(trifluoromethoxy)propoxy]-propionate dispersant (CF3OCF(CF3)CF2OCF(CF3)COONH4)[PMPA] were added to a 0.3 L glass reactor equipped with a stirrer. The reactor contents were then heated to 70 °C to achieve a deoxygenated state. Perfluorooctadiene (CF2=CF(CF2)4CF=CF2) was added in the amounts listed in Table 1, followed by the injection of 0.015 g of ammonium persulfate (APS) initiator dissolved in 2 g of deionized water, bringing the reactor pressure to 0.835 MPaG. A pressure decrease occurred after the initiator injection, indicating the start of polymerization. TFE was added to the reactor while maintaining the pressure, and polymerization continued until approximately 40 g of TFE had reacted completely. Then, the pressure inside the reactor was vented until atmospheric pressure was reached, and the contents were removed from the reactor and cooled. The paraffin in the supernatant was removed from the aqueous dispersion of the fluoropolymer. The solids concentration and the average primary particle size of the primary particles in the resulting aqueous dispersion are shown in Table 1.

[0393] The obtained aqueous dispersion was diluted with deionized water to achieve a solids concentration of approximately 15% by mass. 2.5g of nitric acid was added to 100g of the obtained fluoropolymer aqueous dispersion, and the mixture was stirred to allow it to solidify. The resulting wet powder was filtered and washed again with 3000g of deionized water. This washing operation was repeated three times, followed by drying in a thermal cyclic dryer at 150°C for 18 hours to obtain the fluoropolymer powder. The results are shown in Table 1.

[0394] Synthesis Examples 2-4 (Preparation of Fluoropolymers)

[0395] Except for changing the amount of perfluorooctadiene added as described in Table 1, the aqueous dispersion and powder of the fluoropolymer were obtained in the same manner as in Synthesis Example 1. The results are shown in Table 1.

[0396] Synthesis Example 5 (Preparation of Fluoropolymers)

[0397] In a 0.3 L glass reactor equipped with a stirrer, 150 g of deionized water, 6 g of paraffin wax, and 0.225 g of ammonium 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(trifluoromethoxy)propoxy]-propionate dispersant (CF3OCF(CF3)CF2OCF(CF3)COONH4)[PMPA] were added. The reactor contents were then heated to 70 °C to achieve a deoxygenated state. Next, 4 mg of propane gas and 0.16 g of perfluorooctadiene (CF2=CF(CF2)4CF=CF2) were added. Then, 0.015 g of ammonium persulfate (APS) initiator dissolved in 2 g of deionized water was injected into the reactor, bringing the pressure to 0.835 MPaG. After the initiator was injected, a pressure decrease occurred, and polymerization was observed to begin. TFE was added to the reactor and pressure was maintained. Polymerization continued until approximately 40g of TFE had reacted completely. Afterward, the pressure inside the reactor was vented until atmospheric pressure was reached. The contents were then removed from the reactor and cooled. The supernatant paraffin was removed from the aqueous dispersion of the fluoropolymer.

[0398] The obtained aqueous dispersion was diluted with deionized water to achieve a solids concentration of approximately 20% by mass. 2.5 g of nitric acid was added to 100 g of the obtained fluoropolymer aqueous dispersion, and the mixture was stirred to allow it to solidify. The resulting wet powder was filtered and washed again with 3000 g of deionized water. This washing operation was repeated three times. The powder was then dried in a thermal cyclic dryer at 150°C for 18 hours to obtain the fluoropolymer powder. The results are shown in Table 3.

[0399] Synthesis Example 6 (Preparation of Fluoropolymers)

[0400] Except that the 4 mg propane gas in Synthesis Example 5 was replaced with 2 mg, the aqueous dispersion and powder of the fluoropolymer were obtained in the same manner as in Synthesis Example 5. The results are shown in Table 3.

[0401] Comparative Synthesis Example 1 (Preparation of Fluoropolymers)

[0402] Except for the absence of perfluorooctadiene, aqueous dispersions and powders of fluoropolymers were obtained in the same manner as in Synthesis Example 1. The results are shown in Table 1.

[0403] Comparative Synthesis Example 2

[0404] Perfluorooctadiene was converted to perfluoro[3-(1-methyl-2-vinyloxy-ethoxy)propionitrile] (hereinafter referred to as CNVE), and the drying conditions were set to 24 hours in a vacuum drying oven at 70°C. Otherwise, the aqueous dispersion and powder of the fluoropolymer were obtained in the same manner as in Synthesis Example 1. The results are shown in Table 1.

[0405] Comparative Synthesis Example 3

[0406] Except for the absence of perfluorooctadiene, aqueous dispersions and powders of fluoropolymers were obtained in the same manner as in Synthesis Example 5. The results are shown in Table 3.

[0407]

[0408] Next, examples using the fluoropolymer manufactured above as a filler will be described. The values ​​for each example were measured using the following method.

[0409] <Composition of Fluorinated Elastomers>

[0410] pass 19 The determination was performed using F-NMR and IR analyses.

[0411] Mooney viscosity

[0412] The measurements were performed at 170°C using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES, according to JISK 6300.

[0413] <Crosslinking Properties>

[0414] Using an RPA2000 manufactured by ALPHA TECHNOLOGIES, the crosslinking curve of the obtained composition was determined under the measurement conditions of 180°C, 30 minutes, 1 Hz, and 10% strain, and the minimum torque (ML) and maximum torque (MH) were determined.

[0415] Compression permanent deformation

[0416] The compression set is measured according to the methods described in ASTM D395 or JIS K6262. Using a compression device, the O-rings produced in the examples and comparative examples are compressed at room temperature to a compression ratio of 25% (a 3.5 mm thick (wire diameter) O-ring is compressed to a thickness of 2.625 mm).

[0417] Next, the compression device with the compressed O-ring fixed is placed statically in an electric furnace and left at 200 °C for 70 hours, then the compression device is taken out of the electric furnace. After that, the compression device with the compressed O-ring fixed is placed statically in another electric furnace and left at 70 °C for 24 hours. The O-ring is removed from the compression device, and the removed O-ring is left in a constant temperature chamber and left at 23 °C for 30 minutes to measure the thickness (t2) of the O-ring. The compression set is calculated by the following formula. A small compression set means excellent recovery at low temperature after use at high temperature, indicating excellent performance under conditions close to the O-ring's usage environment.

[0418] Compression set (%) = (t0 - t2) / (t0 - t1) × 100

[0419] t0: The original thickness (mm) of the O-ring

[0420] t1: The thickness (mm) of the spacer

[0421] t2: The thickness (mm) of the O-ring after the compression test

[0422] In the above test, t0 = 3.5 mm and t1 = 2.625 mm.

[0423] <ICP Plasma Weight Loss Rate>

[0424] The O-rings (P24 size) produced in the examples and comparative examples are placed statically in the processing chamber. The plasma generated by a radical generation device is sent into the processing chamber, and the O-rings are exposed under the following plasma irradiation conditions. The ICP plasma weight loss rates of O2 and CF4 are calculated from the masses of the O-rings before and after plasma irradiation.

[0425] (Plasma Irradiation Conditions)

[0426] Radical generation device: ICP high-density plasma device (RIE-101iPH manufactured by SAMCO)

[0427] Gas flow rate: 16 sccm

[0428] Power: 400 W

[0429] Pressure: 2.66 Pa

[0430] Irradiation time: 1 hour

[0431] <NF3 Remote Plasma Weight Reduction Rate>

[0432] The O-rings (P24 size) fabricated in the examples and comparative examples were placed statically in the processing chamber. The plasma generated using a fluorine radical generator was introduced into the processing chamber, and the O-rings were exposed under the following plasma irradiation conditions. The NF3 remote plasma weight reduction rate was calculated from the masses of the O-rings before and after plasma irradiation.

[0433] (Plasma Irradiation Conditions)

[0434] Fluorine radical generator: Astron Atomic Fluorine Generator Model AX7657-2 (manufactured by MKS Corporation)

[0435] Gas flow rate: Ar / NF3 = 1 (L / minute) / 1 (L / minute)

[0436] Pressure: 3 Torr

[0437] Irradiation temperature: 250 °C

[0438] Irradiation time: 12 hours (the position of the O-ring in the chamber was moved every 2 hours)

[0439] (Mass Measurement)

[0440] An electronic analytical balance BP211D (manufactured by Sartorius) was used to measure the masses of the O-rings before and after plasma irradiation. Moreover, the NF3 remote plasma weight reduction rate was calculated by the following formula.

[0441] dW = (W0 - W1) / W0 × 100

[0442] dW: NF3 remote plasma weight reduction rate

[0443] W0: Mass of the O-ring before plasma irradiation

[0444] W1: Mass of the O-ring after plasma irradiation

[0445] Example 1

[0446] 100 parts by mass of a fluorine-containing elastomer (TFE / PMVE / CF2=CFOCF2CF(CF3)OCF2CF2CN = 59.3 / 39.9 / 0.8 (mol%), Mooney viscosity ML(1+20)(170 °C) = 66), 20 parts by mass of the fluorine-containing polymer obtained in Synthesis Example 1, and 0.9 parts by mass of 2,2-bis[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane as a crosslinking agent were kneaded using an open roll to prepare a composition. The results are shown in Table 2.

[0447] The obtained composition was pressed at 180°C for 30 minutes to crosslink, and then heated in an oven at 290°C for 18 hours to crosslink again, producing P24 size O-rings. Using the obtained O-rings, compression set, ICP plasma weight reduction rate, and remote plasma weight reduction rate were measured using the above method. The results are shown in Table 2.

[0448] Examples 2-4

[0449] The composition and O-ring were otherwise obtained in the same manner as in Example 1, except that the fluoropolymers described in Table 2 were used instead of the fluoropolymers obtained in Synthesis Example 1. The results are shown in Table 2.

[0450] Comparative Example 1

[0451] The composition and O-ring were otherwise obtained in the same manner as in Example 1, except that the fluoropolymers described in Table 2 were used instead of the fluoropolymers obtained in Synthesis Example 1. The results are shown in Table 2.

[0452] Comparative Example 2

[0453] The composition was obtained in the same manner as in Example 1, except that the fluoropolymers listed in Table 2 were used instead of the fluoropolymers obtained in Synthesis Example 1. The resulting composition shows MH and ML as listed in Table 2. During the preparation of the composition, a gradual loss of plasticity was observed. The resulting composition was difficult to mold, making it impossible to produce O-rings, measure compression set, ICP plasma weight reduction rate, or remote plasma weight reduction rate.

[0454] [Table 2]

[0455] Table 2

[0456]

[0457] Examples 5-6

[0458] The composition and O-ring were obtained in the same manner as in Example 1, except that the fluoropolymers described in Table 3 were used instead of the fluoropolymers obtained in Synthesis Example 1. The results are shown in Table 3.

[0459] Comparative Example 3

[0460] The composition and O-ring were obtained in the same manner as in Example 1, except that the fluoropolymers described in Table 3 were used instead of the fluoropolymers obtained in Synthesis Example 1. The results are shown in Table 3.

[0461] [Table 3]

[0462] Table 3

[0463]

Claims

1. A fluoropolymer comprising a tetrafluoroethylene unit (1) and a monomer unit (2) derived from a perfluorodiene of general formula (2), CF2=CF(CF2) n CF=CF2 In the formula, n represents an integer from 2 to 10. The content of tetrafluoroethylene unit (1) is 98.0 mol% to 99.999 mol% relative to all monomer units constituting the fluoropolymer. The content of monomer unit (2) is 0.001 mol% to 2.0 mol% relative to all monomer units constituting the fluoropolymer.

2. The fluoropolymer according to claim 1, wherein, The 1030–1040 cm⁻¹ values ​​were obtained through infrared absorption spectroscopy analysis of the fluoropolymer. -1 The peak height h1 at this location is relative to 2360–2370 cm. -1 The spectral intensity ratio of the peak height h0 at the location is greater than 0.001 to h1 / h0.

3. The fluoropolymer according to claim 1 or 2, wherein, The 1780–1800 cm⁻¹ values ​​obtained by infrared absorption spectroscopy analysis of the fluoropolymer were... -1 The peak height h2 at this location is relative to 2360–2370 cm. -1 The spectral intensity ratio of the peak height h0 appearing at a given location is below 0.20 for h2 / h0.

4. The fluoropolymer according to claim 1 or 2, wherein, The peak temperature is above 300°C, which is the temperature corresponding to the maximum value in the differential thermal analysis (DTA) curve obtained by heating the fluoropolymer at a rate of 10°C / minute under atmospheric conditions without heating it to a temperature above 300°C.

5. The fluoropolymer according to claim 1 or 2, wherein, The melt viscosity measured at 380℃ was 1.0 × 10⁻⁶. 3 Mooring ~7.0×10 6 moor.

6. The fluoropolymer according to claim 1 or 2, wherein it is in the form of a powder.

7. An aqueous dispersion comprising the fluoropolymer according to any one of claims 1 to 6.

8. A composition comprising the fluoropolymer of any one of claims 1 to 6 and a polymer different from the fluoropolymer.

9. The composition according to claim 8, wherein, The polymer is a perfluoroelastomer.

10. The composition according to claim 8 or 9, wherein, The content of the fluoropolymer is 0.5 to 100 parts by mass relative to 100 parts by mass of the polymer.

11. The composition according to claim 8 or 9, further comprising at least one selected from the group consisting of inorganic nitrides, organotin compounds, ammonia-generating compounds, and crosslinking agents.

12. A crosslinked compound obtained from the composition of claim 11.

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