Fluoropolymers, aqueous dispersions, compositions and crosslinked products

Abstract

Provided is a fluoropolymer containing a tetrafluoroethylene unit (1) and a monomer unit (2) derived from a perfluoroalkadiene represented by general formula (2) CF2=CF(CF2)nCF=CF2 (in the formula, n represents an integer from 2 to 10), wherein the tetrafluoroethylene unit (1) content is at least 98.0-99.999 mol% relative to all of the monomer units constituting the fluoropolymer, and the monomer unit (2) content is 0.001-2.0 mol% relative to all of the monomer units constituting the fluoropolymer.

Description

[Technical field]

[0001] The present disclosure relates to fluoropolymers, aqueous dispersions, compositions and crosslinked products. [Background technology]

[0002] Patent Document 1 describes a polytetrafluoroethylene molded article obtained by subjecting crosslinkable polytetrafluoroethylene having a reactive functional group such as a cyano group (-CN) to a crosslinking reaction.

[0003] Patent Document 2 describes a fluorine-containing polymer which is a copolymer of a perfluorodiene monomer of formula (1) and at least one other radically polymerizable monomer, and which is characterized in that all or at least one of the other radically polymerizable monomers is a fluorine-containing monomer. CF2 = CFO(CF2CF(CF3)O) n (CF2) m CF=CF2 formula (1) (wherein n and m are each independently an integer from 1 to 3)

[0004] Patent Document 3 describes an elastomer composition for wiper blades, which is characterized by comprising 100 parts by weight of a base elastomer polymer and 5 to 10 parts by weight of irradiation crosslinked PTFE (polytetrafluoroethylene) powder.

[0005] Patent Document 4 describes a composition for a sealing material, which is obtained by blending 5 to 50% by weight of a fluorine-based resin fine powder such as polytetrafluoroethylene powder with a fluorine-based elastomer mainly composed of repeating units derived from a fluoroolefin and a perfluoroalkyl vinyl ether. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2007 / 052664 [Patent Document 2] Japanese Patent Application Publication No. 5-230151 [Patent Document 3] JP 2001-151086 A [Patent Document 4] International Publication No. 97 / 08239 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present disclosure is to provide a fluoropolymer that can be easily produced. Another object of the present disclosure is to provide a composition that can give a crosslinked product that has excellent plasma resistance and small compression set. [Means for solving the problem]

[0008] According to the present disclosure, a tetrafluoroethylene unit (1) and a general formula (2): CF2=CF(CF2) n CF=CF2 (wherein n represents an integer of 2 to 10), the content of tetrafluoroethylene units (1) is 98.0 to 99.999 mol % based on all monomer units constituting the fluoropolymer, and the content of monomer units (2) is 0.001 to 2.0 mol % based on all monomer units constituting the fluoropolymer.

[0009] In the fluoropolymer of the present disclosure, a wavelength of 2360 to 2370 cm obtained by infrared absorption spectrum analysis of the fluoropolymer is -1 The peak height (h0) at 1030-1040cm -1 It is preferable that the spectral intensity ratio (h1 / h0) of the peak height (h1) appearing in the above spectrum is 0.001 or more. In the fluoropolymer of the present disclosure, a wavelength of 2360 to 2370 cm obtained by infrared absorption spectrum analysis of the fluoropolymer is -1The peak height (h0) at 1780-1800 cm -1 It is preferable that the spectral intensity ratio (h2 / h0) of the peak height (h2) appearing in the above spectrum is 0.20 or less. The fluoropolymers of the present disclosure preferably have a peak temperature of 300° C. or greater. The fluoropolymer of the present disclosure has a melt viscosity measured at 380° C. of 1.0×10 3 ~7.0×10 6 It is preferably poise. The fluoropolymer of the present disclosure is preferably in powder form.

[0010] The present disclosure also provides an aqueous dispersion containing the above-described fluoropolymer.

[0011] Also, according to the present disclosure, there is provided a composition containing the above-mentioned fluoropolymer (hereinafter sometimes referred to as fluoropolymer (P)) and a polymer (E) different from the fluoropolymer (P).

[0012] In the composition of the present disclosure, it is preferred that the polymer (E) is a perfluoroelastomer. In the composition of the present disclosure, the content of the fluoropolymer (P) is preferably 0.5 to 100 parts by mass based on 100 parts by mass of the polymer (E). The composition of the present disclosure preferably further contains at least one selected from the group consisting of inorganic nitrides, organotin compounds, compounds that generate ammonia, and crosslinking agents.

[0013] The present disclosure also provides a crosslinked product obtained from the above composition. Effect of the Invention

[0014] According to the present disclosure, a fluoropolymer that can be easily produced can be provided. Furthermore, according to the present disclosure, it is possible to provide a composition which is excellent in plasma resistance and which can give a crosslinked product with small compression set. [Brief description of the drawings]

[0015] [Figure 1] 1 is an infrared absorption spectrum of the fluoropolymer obtained in Synthesis Example 4. The horizontal axis indicates the wave number (cm-1), and the vertical axis indicates the absorbance (A) (%). [Diagram 2] FIG. 2 is an infrared absorption spectrum of the fluoropolymer obtained in Comparative Synthesis Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Specific embodiments of the present disclosure will be described in detail below, but the present disclosure is not limited to the following embodiments.

[0017] The fluoropolymers of the present disclosure contain tetrafluoroethylene (TFE) units (1) and monomeric units (2).

[0018] In response to this, Patent Document 1 describes that a PTFE resin that is less prone to deformation than conventional PTFE resins can be obtained by introducing a reactive functional group such as a cyano group (-CN) into polytetrafluoroethylene (PTFE) and crosslinking the resulting PTFE resin. However, when a reactive functional group such as a cyano group is introduced into PTFE, the reactive functional group is easily hydrolyzed, and an improvement in storage stability is desired.

[0019] Patent Document 2 also describes a method for obtaining a copolymer by copolymerizing a perfluorodiene monomer having the structure of the above-mentioned formula (1). Such a perfluorodiene monomer has a problem in that it is highly reactive and difficult to control the copolymerization reaction.

[0020] Patent Document 3 describes that irradiated cross-linked PTFE obtained by irradiating with an electron beam exhibits abrasion resistance 1000 times or more higher than that of uncross-linked PTFE. When PTFE is irradiated with an electron beam, the PTFE decomposes simultaneously with cross-linking, which causes a problem of reduced heat resistance of PTFE. In addition, it is necessary to introduce a device for irradiating with an electron beam, making it difficult to reduce production costs.

[0021] The monomer unit (2) contained in the fluoropolymer of the present disclosure has the general formula (2): CF2=CF(CF2) n CF=CF2 (wherein n is an integer of 2 to 10) is copolymerized with TFE to introduce it into the fluoropolymer. The copolymerization reaction between TFE and perfluoroalkadiene is relatively easy to control, so the fluoropolymer of the present disclosure can be easily produced. In addition, since a reactive functional group that is easily hydrolyzed is not introduced into the fluoropolymer, the fluoropolymer of the present disclosure is also excellent in storage stability. Furthermore, since the fluoropolymer of the present disclosure is not modified by radiation exposure, the fluoropolymer of the present disclosure has excellent heat resistance and at the same time, shows improved creep resistance compared to uncrosslinked PTFE. The fluoropolymer of the present disclosure may contain two or more types of monomer units derived from perfluoroalkadiene represented by general formula (2) as the monomer unit (2).

[0022] In the general formula (2), n represents an integer of 2 to 10. n is preferably an integer of 3 to 9, and more preferably an integer of 4 to 8. From the viewpoint of ease of synthesis of the perfluoroalkadiene, n is preferably 2, 4, 6, 8, or 10, more preferably 2, 4, 6, or 8, further preferably 4, 6, or 8, and particularly preferably 4 or 8.

[0023] The perfluoroalkadiene represented by general formula (2) is preferably at least one selected from 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.

[0024] Perfluoroalkadiene does not contain CH bond, so by polymerizing perfluoroalkadiene, the same structure as TFE unit can be introduced into polymer chain.This reason can also explain the excellent heat resistance of the fluoropolymer of the present disclosure.

[0025] The content of TFE units in the fluoropolymer is 98.0 to 99.999 mol% based on the total monomer units constituting the fluoropolymer. The content of TFE units is preferably 98.5 mol% or more, more preferably 98.8 mol% or more, and preferably 99.995 mol% or less, more preferably 99.990 mol% or less, since heat resistance can be improved while maintaining excellent storage stability and creep resistance.

[0026] The content of the monomer unit (2) in the fluoropolymer is 0.001 to 2.0 mol% based on the total monomer units constituting the fluoropolymer. The content of the 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, and is 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, since storage stability and creep resistance can be improved while maintaining excellent heat resistance.

[0027] The content of the monomer unit in the fluoropolymer can be calculated by appropriately combining NMR and FT-IR depending on the type of monomer.

[0028] The fluoropolymers of the present disclosure may contain monomeric units derived from other monomers other than TFE and perfluoroalkadienes.

[0029] The other monomer is not particularly limited as long as it is a monomer copolymerizable with TFE and a perfluoroalkadiene, and examples thereof include perfluoroolefins such as hexafluoropropylene [HFP], etc.; chlorofluoroolefins such as chlorotrifluoroethylene [CTFE], etc.; hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VDF], etc.; fluoroalkyl vinyl ethers; fluoroalkyl allyl ethers; perfluoroalkyl ethylenes; and ethylene.

[0030] The fluoropolymer of the present disclosure has a peak at 1030 to 1040 cm in the infrared absorption spectrum obtained when the fluoropolymer is subjected to infrared absorption spectrum analysis. -1 It is preferable that the fluoropolymer shows a characteristic peak at 2360 to 2370 cm obtained by infrared absorption spectrum analysis. -1 The peak height (h0) at 1030-1040cm -1 The spectral intensity ratio (h1 / h0) of the peak height (h1) appearing in is preferably 0.001 or more, more preferably 0.005 or more, preferably 2.500 or less, more preferably 1.500 or less, even more preferably 1.000 or less, and particularly preferably 0.650 or less.

[0031] 1030~1040cm -1 The absorption peak appearing at 1030 to 1040 cm is presumed to be a peak derived from the C-C bond of the branched portion of the polymer chain formed by copolymerization of perfluoroalkadiene, and the magnitude of the spectral intensity ratio (h1 / h0) is presumed to represent the amount of the branched portion structure derived from the perfluoroalkadiene introduced into the polymer chain. When perfluoroalkadiene is polymerized, a structure similar to the TFE unit is presumed to be introduced into the polymer chain, but fluoropolymers containing monomer units derived from perfluoroalkadiene have a peak at 1030 to 1040 cm. -1A characteristic peak is shown around the fluoropolymer of the present disclosure, and conventional PTFE does not show a similar peak. Therefore, the fluoropolymer of the present disclosure has a structure that is clearly different from that of conventional PTFE. The fluoropolymer contains a monomer unit derived from perfluoroalkadiene, and shows such a characteristic peak, and has excellent storage stability, heat resistance and creep resistance.

[0032] The fluoropolymer of the present disclosure has a peak at 1780 to 1800 cm in the infrared absorption spectrum obtained when the fluoropolymer is subjected to infrared absorption spectroscopy. -1 It is preferable that the fluoropolymer does not show a noticeable peak at 2360 to 2370 cm obtained by infrared absorption spectrum analysis. -1 The peak height (h0) at 1780-1800 cm -1 The spectral intensity ratio (h2 / h0) of the peak height (h2) appearing in the above is preferably 0.25 or less, more preferably 0.20 or less, and preferably 0.15 or more.

[0033] The magnitude of the spectral intensity ratio (h2 / h0) is presumed to represent the amount of double bonds in the side chains of the fluoropolymer in addition to the amount of C-F bonds contained in the fluoropolymer chain. When the fluoropolymer has double bonds in the side chains, the infrared absorption spectrum of 1780 to 1800 cm -1 Strong absorption is observed at 100 nm. Fluoropolymers with a small spectral intensity ratio (h2 / h0) have no or almost no double bonds in the side chains, so that, for example, even when used in a mixture with other polymers, they do not react with the other polymers and can continue to exist extremely stably in the composition.

[0034] From the viewpoint of heat resistance, the peak temperature of the fluoropolymer is preferably 300°C or higher, more preferably 310°C or higher, even more preferably 320°C or higher, and is preferably 347°C or lower, more preferably 345°C or lower.

[0035] It is also preferred that the fluoropolymer has a relatively high peak temperature. The peak temperature of the fluoropolymer is preferably 333° C. or higher, more preferably 335° C. or higher, and preferably 347° C. or lower, more preferably 345° C. or lower. Fluoropolymers with relatively high peak temperatures tend to exhibit fibrillation and non-melt processability.

[0036] It is also preferred that the fluoropolymer has a relatively low peak temperature. The peak temperature of the fluoropolymer is preferably 322° C. or higher, more preferably 324° C. or higher, and preferably 333° C. or lower, more preferably 332° C. or lower. Fluoropolymers with relatively low peak temperatures tend to be non-fibrillating and tend to be melt processable.

[0037] The peak temperature can be measured by weighing out about 10 mg of fluoropolymer powder that has not been heated to a temperature of 300°C or higher, placing it in a dedicated aluminum pan, and using a TG / DTA (thermogravimetric / differential thermal analyzer). The peak temperature can be identified as the temperature that corresponds to the maximum value that appears on a differential thermal (DTA) curve obtained by heating a fluoropolymer that has not been heated to a temperature of 300°C or higher in air at a rate of 10°C / min using a TG / DTA (thermogravimetric / differential thermal analyzer).

[0038] From the viewpoint of heat resistance, the 1.0% by mass 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% by mass weight loss temperature may be 500° C.

[0039] The 1.0% by mass weight loss temperature can be measured by precisely weighing out about 10 mg of fluoropolymer powder that has not been heated to a temperature of 300°C or higher, placing it in a dedicated aluminum pan, and using a TG / DTA (thermogravimetric / differential thermal analyzer). The 1.0% by mass weight loss temperature can be determined as the temperature at which the weight has decreased by 1.0% by mass when the aluminum pan is heated in the air in the temperature range from 25°C to 600°C at a rate of 10°C / min.

[0040] The specific gravity of the fluoropolymer is preferably 2.130 to 2.230, and more preferably 2.130 to 2.190.

[0041] The specific gravity can be measured by the SSG method or the water displacement method. The SSG can be measured by the water displacement method according to ASTM D 792 using a sample molded according to ASTM D 4895-89.

[0042] The fluoropolymer according to one embodiment has a fibrillating property. The fluoropolymer having the fibrillating property can be molded by paste extrusion molding by utilizing the fibrillating property. Furthermore, the fluoropolymer can be extruded by paste extrusion molding, and the extrudate can be rolled to be molded into a sheet, or the extrudate can be stretched to be molded into a porous body.

[0043] The fluoropolymer according to one embodiment does not have fibrillating properties. Since the fluoropolymer without fibrillating properties has excellent chemical stability, extremely low surface energy, and is less likely to form fibrils, it is suitable for use as an additive for improving the slipperiness and texture of the coating surface in the manufacture of plastics, inks, cosmetics, paints, greases, office automation equipment components, toners, and the like (see, for example, JP-A-10-147617).

[0044] The presence or absence of fibrillation properties can be judged by "paste extrusion," a typical method for molding "high molecular weight PTFE powder," a powder made from a TFE polymer. Paste extrusion is usually possible because high molecular weight PTFE has fibrillation properties. If the unsintered molded product obtained by paste extrusion has no substantial strength or elongation, for example, if it breaks when pulled with an elongation of 0%, it can be considered to have no fibrillation properties.

[0045] In one embodiment, the fluoropolymer has non-melt processability. Non-melt processable fluoropolymers have a tendency to exhibit fibrillation.

[0046] The fluoropolymer according to one embodiment does not have non-melt processability. The fluoropolymer that does not have non-melt processability tends not to generate fibrils. By using the fluoropolymer that does not have non-melt processability (the fluoropolymer that has melt processability) in the composition of the present disclosure described later, the plasma resistance (especially the durability against NF3 remote plasma) of the crosslinked product obtained from the composition can be improved.

[0047] By non-melt processable it is meant that the melt flow rate cannot be measured according to ASTM D 1238 and D 2116 above the peak temperatures noted above.

[0048] The fluoropolymer according to one embodiment has a melt viscosity of 1.0×10 measured at 380° C. 3 ~7.0×10 6 poise, preferably 1.0×10 4 ~5.0×10 6 poise, and more preferably 1.0×10 5 ~2.0×10 6 By using a fluoropolymer having a melt viscosity within the above range in the composition of the present disclosure described below, the plasma resistance (particularly the durability against NF3 remote plasma) of the crosslinked product obtained from the composition can be greatly improved.

[0049] The peak temperature, fibrillation property and non-melt processability of fluoropolymer can be adjusted by adjusting the conditions of polymerization of fluoromonomer to produce fluoropolymer.For example, by appropriately selecting the conditions of polymerization of fluoromonomer so as to increase the molecular weight of the obtained fluoropolymer, the peak temperature of fluoropolymer can be increased, and a fluoropolymer having fibrillation property and non-melt processability can be produced.By using a chain transfer agent during polymerization of fluoromonomer, and appropriately selecting the type and amount of chain transfer agent, the peak temperature of fluoropolymer can be decreased, and a fluoropolymer having no fibrillation property and non-melt processability can be produced.

[0050] The fluoropolymer of the present disclosure can be produced by a polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. A method for producing a fluoropolymer by emulsion polymerization will be described.

[0051] The fluoropolymer of the present disclosure can be produced, for example, by polymerizing TFE and perfluoroalkadiene in the presence of an aqueous medium, a polymerization initiator and a surfactant. More specifically, a reactor is charged with TFE and perfluoroalkadiene, an aqueous medium, a surfactant and other additives as necessary, the reactor contents are stirred, and the reactor is maintained at a predetermined polymerization temperature, and then a predetermined amount of polymerization initiator is added to start the polymerization reaction, thereby polymerizing TFE and perfluoroalkadiene. After the polymerization reaction starts, TFE, perfluoroalkadiene, polymerization initiator, chain transfer agent, etc. may be added according to the purpose.

[0052] The aqueous medium is a reaction medium for polymerization and means a liquid containing water. The aqueous medium is not particularly limited as long as it contains water, and may contain water and, for example, a fluorine-free organic solvent such as an alcohol, ether, or ketone, and / or a fluorine-containing organic solvent having a boiling point of 40° C. or lower.

[0053] The polymerization initiator is not particularly limited as long as it can generate radicals within the polymerization temperature range, and known oil-soluble and / or water-soluble polymerization initiators can be used. Furthermore, it can also be combined with a reducing agent or the like to initiate polymerization as a redox initiator.

[0054] The amount of the polymerization initiator added is preferably 1 ppm by mass or more, more preferably 5 ppm by mass or more, and preferably 5000 ppm by mass or less, more preferably 1000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the aqueous medium.

[0055] The polymerization initiator is preferably a water-soluble radical polymerization initiator, and examples thereof include ammonium salts, potassium salts, and sodium salts of persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, and percarbonic acid, organic peroxides such as disuccinic acid peroxide and diglutaric acid peroxide, t-butyl permaleate, and t-butyl hydroperoxide.

[0056] The surfactant may be a fluorine-containing surfactant. Examples of the fluorine-containing surfactant include: General formula:X-(CF2) m1 -COOX (wherein X represents H or F, m1 represents an integer of 3 to 5, and X represents H, NH4 or an alkali metal atom), General formula: CF3OCF(CF3)CF2OCF(CF3)COOX (wherein X represents H, NH4 or an alkali metal atom).

[0057] The amount of the surfactant added is preferably 10 ppm by mass to 10% by mass relative to the aqueous medium.

[0058] In the polymerization, a chain transfer agent may be used, for example, 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 mercaptans, various halogenated hydrocarbons such as carbon tetrachloride, and cyclohexane.

[0059] During the polymerization, additives such as a buffering agent, a pH adjusting agent, a stabilizing aid, and a dispersion stabilizer can be used.

[0060] As the stabilizing aid, paraffin wax, fluorine-based oil, fluorine-based solvent, silicone oil, etc. are preferable. The stabilizing aid may be used alone or in combination of two or more. As the stabilizing aid, paraffin wax is more preferable. The paraffin wax may be liquid, semi-solid, or solid at room temperature, but is preferably a saturated hydrocarbon having 12 or more carbon atoms. The melting point of the paraffin wax is usually preferably 40 to 65°C, more preferably 50 to 65°C.

[0061] The amount of the stabilizing agent used is preferably 0.1 to 12% by mass based on the aqueous medium.

[0062] The polymerization can be carried out under normal pressure and temperature. Usually, the polymerization temperature is 5 to 120°C, and the polymerization pressure is 0.05 to 10 MPaG. The polymerization temperature and polymerization pressure are appropriately determined depending on the type of monomer, the molecular weight of the desired fluoropolymer, the reaction rate, etc.

[0063] By polymerization of TFE and perfluoroalkadiene in an aqueous medium, an aqueous dispersion containing a fluoropolymer is obtained. The content of the fluoropolymer in the aqueous dispersion after polymerization is usually 8 to 50 mass % based on the aqueous dispersion.

[0064] The fluoropolymer can be recovered by aggregating the fluoropolymer in the aqueous dispersion. The method of aggregating the fluoropolymer is not particularly limited. For example, the fluoropolymer can be aggregated by vigorously stirring the aqueous dispersion. The fluoropolymer may be aggregated by adding 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 as coagulants to the aqueous dispersion and stirring the mixture. After aggregating the fluoropolymer, the aggregated fluoropolymer can be recovered as a wet polymer.

[0065] The obtained wet polymer may be dried. The drying temperature is preferably 10 to 300°C, more preferably 100 to 300°C. By sufficiently drying, a fluoropolymer powder can be obtained. The fluoropolymer of the present disclosure may be an aqueous dispersion in which fluoropolymer particles are dispersed in an aqueous medium, or may be a fluoropolymer powder.

[0066] The fluoropolymer of the present disclosure (hereinafter sometimes referred to as fluoropolymer (P)) can be used for various applications.

[0067] The fluoropolymer of the present disclosure can be easily produced and has excellent storage stability, heat resistance, and creep resistance, and therefore can be suitably used for various molded products. In particular, when the fluoropolymer of the present disclosure has fibrillating properties or is non-melt processable, it can be suitably used for various molded products.

[0068] The fluoropolymer may be molded to obtain a molded product by a conventional method, for example, a known method such as compression molding, ram extrusion molding, or paste extrusion molding.

[0069] Specific examples of molded articles include packings, gaskets, tubes, linings, coatings, insulating tapes, bearings, roof membranes for air domes, gas / liquid separation membranes, separators, support membranes, etc. The shape of the molded article is not particularly limited, but may be a tube, film, sheet, fiber, porous membrane, etc.

[0070] In addition, the fluoropolymer of the present disclosure can be easily produced and has excellent storage stability, heat resistance and creep resistance, so that it can be suitably used as a filler, for example. The fluoropolymer of the present disclosure is obtained by polymerizing perfluoroalkadiene, but the double bond of the perfluoroalkadiene disappears by polymerization, so the fluoropolymer of the present disclosure has no double bond or has almost no double bond. Therefore, the fluoropolymer of the present disclosure functions as a filler but does not function as a crosslinking agent.

[0071] The fluoropolymer of the present disclosure can also be used as an additive. In particular, when the fluoropolymer of the present disclosure does not have fibrillation properties or does not have non-melt processability, the fluoropolymer of the present disclosure can be suitably used as an additive.

[0072] The fluoropolymer of the present disclosure can be suitably used as a molding material, an additive for modifying ink, cosmetics, paint, grease, office automation equipment components, toner, etc., an additive for plating solutions, etc. Examples of the molding material include engineering plastics such as polyoxybenzoyl polyester, polyimide, polyamide, polyamideimide, polyacetal, polycarbonate, and polyphenylene sulfide.

[0073] The fluoropolymer of the present disclosure can be suitably used as an additive to molding materials, for example, in applications such as improving the non-stickiness and sliding properties of copy rolls, improving the texture of engineering plastic molded products such as furniture surface sheets, automobile dashboards, and home appliance covers, improving the slipperiness and wear resistance of machine parts that generate mechanical friction such as light-load bearings, gears, cams, push-button phone buttons, projectors, camera parts, and sliding materials, and as a processing aid for engineering plastics.

[0074] The fluoropolymer of the present disclosure can be used as an additive for paints to improve the slipperiness of varnishes and paints.The fluoropolymer of the present disclosure can be used as an additive for cosmetics to improve the slipperiness of cosmetics such as foundations.

[0075] The fluoropolymers of the present disclosure are also suitable for applications in which they improve the oil or water repellency of waxes and the like, and for applications in which they improve the slip properties of greases and toners.

[0076] The fluoropolymer of the present disclosure can also be used as an electrode binder for secondary batteries or fuel cells, a hardness adjuster for electrode binders, a water repellent treatment agent for electrode surfaces, and the like.

[0077] The present disclosure also relates to a composition containing a fluoropolymer (P) and a polymer (E) different from the fluoropolymer (P). The fluoropolymer (P) contained in the composition of the present disclosure is easy to produce, and is excellent in storage stability, heat resistance, and creep resistance. Therefore, the composition of the present disclosure can be produced inexpensively, and by using the composition of the present disclosure, a crosslinked product having excellent plasma resistance and small compression set can be obtained even after use under severe conditions.

[0078] The polymer (E) may be a resin, an elastomer, or the like.

[0079] Examples of resins include fluororesin, polyamide resin, polyolefin resin, vinyl chloride resin, polyurethane resin, polyester resin, polyaramid resin, polyimide resin, polyamideimide resin, polyphenylene oxide resin, polyacetal resin, polycarbonate resin, acrylic resin, styrene resin, acrylonitrile / butadiene / styrene resin (ABS), cellulose resin, polyether ether ketone resin (PEEK), polysulfone resin, polyethersulfone resin (PES), polyetherimide resin, resin made of ethylene / vinyl alcohol copolymer, polyphenylene sulfide resin, polybutylene naphthalate resin, polybutylene terephthalate resin, and polyphthalamide (PPA).

[0080] Examples of fluororesins include TFE / perfluoro(alkyl vinyl ether) copolymers (PFA), TFE / hexafluoropropylene copolymers (FEP), ethylene / TFE copolymers (ETFE), ethylene / TFE / hexafluoropropylene copolymers, polychlorotrifluoroethylene, chlorotrifluoroethylene / TFE copolymers, ethylene / chlorotrifluoroethylene copolymers, polyvinylidene fluoride (PVdF), TFE / vinylidene fluoride copolymers, and polyvinyl fluoride.

[0081] The polymer (E) is preferably an elastomer. Examples of the elastomer include diene rubbers such as acrylonitrile-butadiene rubber (NBR) or its hydrogenated product (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), natural rubber (NR), and isoprene rubber (IR), as well as ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, epichlorohydrin rubber, acrylic rubber, chlorinated polyethylene (CPE), polyblends of acrylonitrile-butadiene rubber and vinyl chloride (PVC-NBR), ethylene propylene diene rubber (EPDM), chlorosulfonated polyethylene (CSM), and fluorine-containing elastomers.

[0082] The polymer (E) is preferably a fluorine-containing elastomer. The fluorine-containing elastomer may be a partially fluorinated elastomer or a perfluoroelastomer, but is preferably a perfluoroelastomer because it has excellent chemical resistance and heat resistance and maximizes the synergistic effect when used in combination with the fluoropolymer (P).

[0083] In the present disclosure, a partially fluorinated elastomer is a fluoropolymer which contains fluoromonomer units and has a perfluoromonomer unit content of less than 90 mol% relative to all monomer units, and which has a glass transition temperature of 20°C or lower and a melting peak (ΔH) magnitude of 4.5 J / g or less.

[0084] In the present disclosure, a perfluoroelastomer is a fluoropolymer having a perfluoromonomer unit content of 90 mol% or more relative to all monomer units, a glass transition temperature of 20°C or less, a melting peak (ΔH) magnitude of 4.5 J / g or less, and a fluorine atom concentration of 71 mass% or more. In the present disclosure, the concentration of fluorine atoms contained in the fluoropolymer is determined by calculating the concentration of fluorine atoms (mass%) contained in the fluoropolymer from the type and content of each monomer constituting the fluoropolymer.

[0085] In the present disclosure, a perfluoromonomer is a monomer that does not contain a carbon atom-hydrogen atom bond in the molecule. The perfluoromonomer may be a monomer in which some of the fluorine atoms bonded to the carbon atom are replaced with chlorine atoms, in addition to carbon atoms and fluorine atoms, and may also have nitrogen atoms, oxygen atoms, and sulfur atoms in addition to carbon atoms. The perfluoromonomer is preferably a monomer in which all hydrogen atoms are replaced with fluorine atoms. The perfluoromonomer does not include a monomer that provides a crosslinking site.

[0086] Examples of the partially fluorinated elastomer include vinylidene fluoride (VdF)-based fluororubber, tetrafluoroethylene (TFE) / propylene (Pr)-based fluororubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF)-based fluororubber, ethylene / hexafluoropropylene (HFP)-based fluororubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF)-based fluororubber, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE)-based fluororubber, etc. Among these, at least one selected from the group consisting of vinylidene fluoride-based fluororubber and tetrafluoroethylene / propylene-based fluororubber is preferable.

[0087] The vinylidene fluoride-based fluororubber is preferably a copolymer consisting of 45 to 85 mol % of vinylidene fluoride and 55 to 15 mol % of at least one other monomer copolymerizable with vinylidene fluoride, and more preferably a copolymer consisting of 50 to 80 mol % of vinylidene fluoride and 50 to 20 mol % of at least one other monomer copolymerizable with vinylidene fluoride.

[0088] In the present disclosure, the content of each monomer constituting the fluorine-containing elastomer can be calculated by an appropriate combination of NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0089] Examples of at least one other monomer copolymerizable with the vinylidene fluoride include TFE, HFP, fluoroalkyl vinyl ether, chlorotrifluoroethylene (CTFE), trifluoroethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, and a monomer represented by the general formula (11): CHX 11 =CX 11 Rf 11 (Wherein, two X 11 One of them is H and the other is F, and Rf 11is a straight-chain or branched fluoroalkyl group having 1 to 12 carbon atoms), a fluoromonomer represented by the general formula (12): CH2=CH-(CF2) n -X 12 (In the formula, X 12 is H or F, and n is an integer of 3 to 10. Fluoromonomers represented by the formula (I) above; monomers which provide crosslinking sites; and non-fluorinated monomers such as ethylene, propylene, and alkyl vinyl ethers. These can be used alone or in any combination. Of these, it is preferable to use at least one selected from the group consisting of TFE, HFP, fluoroalkyl vinyl ether, and CTFE.

[0090] The fluoroalkyl vinyl ethers include General formula (13): CF2=CF-ORf 13 (In the formula, Rf 13 represents a perfluoroalkyl group having 1 to 8 carbon atoms; General formula (14): CF2=CFOCF2ORf 14 (In the formula, Rf 14 is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or a linear or branched perfluorooxyalkyl group having 2 to 6 carbon atoms and containing 1 to 3 oxygen atoms), and General formula (15): CF2=CFO(CF2CF(Y 15 )O) m (CF2) n F (In the formula, Y 15 represents a fluorine atom or a trifluoromethyl group; m is an integer of 1 to 4; and n is an integer of 1 to 4. It is preferable that the fluoromonomer is at least one selected from the group consisting of the following:

[0091] Specific examples of vinylidene fluoride-based fluororubbers include VdF / HFP-based rubbers, VdF / HFP / TFE-based rubbers, VdF / CTFE-based rubbers, VdF / CTFE / TFE-based rubbers, VdF / fluoromonomer-based rubbers represented by general formula (11), VdF / fluoromonomer / TFE-based rubbers represented by general formula (11), VdF / perfluoro(methyl vinyl ether) [PMVE]-based rubbers, VdF / PMVE / TFE-based rubbers, VdF / PMVE / TFE / HFP-based rubbers, etc. As the VdF / fluoromonomer-based rubbers represented by general formula (11), VdF / CH2=CFCF3-based rubbers are preferred, and as the VdF / fluoromonomer / TFE-based rubbers represented by general formula (11), VdF / TFE / CH2=CFCF3-based rubbers are preferred.

[0092] The VdF / CH2=CFCF3 rubber is preferably a copolymer consisting of 40 to 99.5 mol % of VdF and 0.5 to 60 mol % of CH2=CFCF3, and more preferably a copolymer consisting of 50 to 85 mol % of VdF and 15 to 50 mol % of CH2=CFCF3.

[0093] The above-mentioned tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer consisting of 45 to 70 mol % of tetrafluoroethylene, 55 to 30 mol % of propylene, and 0 to 5 mol % of a fluoromonomer that provides a crosslinking site.

[0094] The fluorine-containing elastomer may be a perfluoroelastomer. The perfluoroelastomer is preferably at least one selected from the group consisting of perfluoroelastomers containing TFE units, such as TFE / fluoromonomer copolymers represented by general formula (13), (14) or (15), and TFE / fluoromonomer copolymers representing general formula (13), (14) or (15) / monomer copolymers providing crosslinking sites.

[0095] In the case of a TFE / PMVE copolymer, the composition is preferably 45-90 / 10-55 (mol %), more preferably 55-80 / 20-45, and further preferably 55-70 / 30-45.

[0096] In the case of TFE / PMVE / a monomer copolymer that gives a crosslinking site, the ratio is preferably 45-89.9 / 10-54.9 / 0.01-4 (mol %), more preferably 55-77.9 / 20-49.9 / 0.1-3.5, and further preferably 55-69.8 / 30-44.8 / 0.2-3.

[0097] In the case of a fluoromonomer copolymer having TFE / carbon number of 4 to 12 and represented by general formula (13), (14) or (15), the ratio is preferably 50 to 90 / 10 to 50 (mol %), more preferably 60 to 88 / 12 to 40, and further preferably 65 to 85 / 15 to 35.

[0098] In the case of TFE / fluoromonomer having 4 to 12 carbon atoms represented by general formula (13), (14) or (15) / monomer copolymer providing a crosslinking site, the ratio is preferably 50 to 89.9 / 10 to 49.9 / 0.01 to 4 (mol %), more preferably 60 to 87.9 / 12 to 39.9 / 0.1 to 3.5, and even more preferably 65 to 84.8 / 15 to 34.8 / 0.2 to 3. Outside these composition ranges, the rubber elastic properties are lost and the properties tend to become more like those of a resin.

[0099] The perfluoroelastomer is preferably at least one selected from the group consisting of TFE / fluoromonomer represented by general formula (15) / monomer copolymer providing a crosslinking moiety, TFE / fluoromonomer copolymer represented by general formula (15), TFE / fluoromonomer copolymer represented by general formula (13), and TFE / fluoromonomer represented by general formula (13) / monomer copolymer providing a crosslinking moiety.

[0100] Examples of the perfluoroelastomer 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.

[0101] The monomer that provides a crosslinking site is a monomer (cure site monomer) having a crosslinkable group that provides the fluorine-containing elastomer with a crosslinking site for forming a crosslink with a crosslinking agent.

[0102] Examples of monomers that provide crosslinking sites include: General formula (16):CX 4 2=CX 5 R f 2 X 6 (In the formula, X 4 , X 5 are each independently H, F or an alkyl group having 1 to 5 carbon atoms, and R f 2 is a linear or branched alkylene or oxyalkylene group which may have one or more ether-bonded oxygen atoms and which may have an aromatic ring, and in which some or all of the hydrogen atoms may be substituted with fluorine atoms; X 6 is an iodine atom, a bromine atom, a nitrile group, a carboxyl group, an alkoxycarbonyl group, a hydroxyl group, a vinyl group, an azide group, a sulfonyl azide group, a carbonyl azide group, or an alkyne group. The alkyne group may be an ethynyl group.

[0103] Among the monomers that provide crosslinking sites are: General formula (17):CX 16 2=CX 16 -Rf 16 CHR 16 X 17 (In the formula, X 16 Each independently represents a hydrogen atom, a fluorine atom, or CH3, Rf 16represents a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group or a perfluoro(poly)oxyalkylene group; R 16 is a hydrogen atom or CH3, X 17 is an iodine atom or a bromine atom), General formula (18):CX 16 2=CX 16 -Rf 17 X 17 (In the formula, X 16 Each independently represents a hydrogen atom, a fluorine atom, or CH3, Rf 17 represents a fluoroalkylene group, a perfluoroalkylene group, a fluoro(poly)oxyalkylene group or a perfluoro(poly)oxyalkylene group; X 17 is an iodine atom or a bromine atom), General formula (19): CF2=CFO(CF2CF(CF3)O) m (CF2) n -X 18 (In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, X 18 is a cyano group, an azide group, a sulfonyl azide group, a carbonyl azide group, a carboxyl group, an alkoxycarbonyl group, an alkyne group, an iodine atom, a bromine atom, or -CHI), General formula (20): CH2=CFCF2O(CF(CF3)CF2O) m (CF(CF3)) n -X 19 (In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, X 19 is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CHOH), and General formula (21):CR 20 2=CR 20 -Z-CR 20 =CR 20 2 (In the formula, R 20are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z is a linear or branched alkylene group having 1 to 18 carbon atoms, which may have an oxygen atom, a cycloalkylene group having 3 to 18 carbon atoms, an at least partially fluorinated alkylene group or oxyalkylene group having 1 to 10 carbon atoms, or -(Q) p -CF2O-(CF2CF2O) m (CF2O) n -CF2-(Q) p - (wherein Q is an alkylene group or an oxyalkylene group, p is 0 or 1, and m / n is 0.2 to 5), and is a (per)fluoropolyoxyalkylene group having a molecular weight of 500 to 10,000.

[0104] X 16 is preferably a fluorine atom. 16 and Rf 17 R is preferably a perfluoroalkylene group having 1 to 5 carbon atoms. 16 is preferably a hydrogen atom. 18 is preferably a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CH2I. 19 is preferably a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or -CHOH.

[0105] Monomers that provide crosslinking sites include CF2=CFOCF2CF(CF3)OCF2CF2CN, CF2=CFOCF2CF(CF3)OCF2CF2COOH, CF2=CFOCF2CF(CF3)OCF2CF2CH2I, CF2=CFOCF2CF2CH2I, CH2=CFCF2OCF(CF3)CF2OCF(CF3)CN, CH2=CFCF2OCF(CF3)CF2OCF(CF3)COOH, CH2=CFCF2OCF(C F3) is preferably at least one selected from the group consisting of CF2OCF(CF3)CH2OH, CH2=CHCF2CF2I, CH2=CH(CF2)2CH=CH2, CH2=CH(CF2)6CH=CH2, and CF2=CFO(CF2)5CN, and more preferably at least one selected from the group consisting of CF2=CFOCF2CF(CF3)OCF2CF2CN and CF2=CFOCF2CF2CH2I.

[0106] The above-mentioned fluorine-containing elastomer has a glass transition temperature of preferably −70° C. or higher, more preferably −60° C. or higher, and even more preferably −50° C. or higher, from the viewpoint of excellent compression set characteristics at high temperatures. Also, from the viewpoint 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.

[0107] The glass transition temperature can be determined by obtaining a DSC curve using a differential scanning calorimeter (DSC822e, manufactured by Mettler Toledo) by heating 10 mg of a sample at a rate of 10°C / min, and by determining the temperature that indicates the midpoint between the two intersection points of an extension of the baseline before and after the second-order transition of the DSC curve and a tangent to the inflection point of the DSC curve.

[0108] The fluorine-containing elastomer preferably has a Mooney viscosity ML(1+20) at 170° C. of 30 or more, more preferably 40 or more, and even more preferably 50 or more, in terms of good heat resistance. Also, in terms of good processability, it is preferably 150 or less, more preferably 120 or less, and even more preferably 110 or less.

[0109] The fluorine-containing elastomer preferably has a Mooney viscosity ML(1+20) at 140° C. of 30 or more, more preferably 40 or more, and even more preferably 50 or more, in terms of good heat resistance. Also, in terms of good processability, it is preferably 180 or less, more preferably 150 or less, and even more preferably 110 or less.

[0110] The fluorine-containing elastomer preferably has a Mooney viscosity ML(1+10) at 100° C. of 10 or more, more preferably 20 or more, and even more preferably 30 or more, in terms of good heat resistance. Also, in terms of good processability, it is preferably 120 or less, more preferably 100 or less, and even more preferably 80 or less.

[0111] The Mooney viscosity can be measured using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES at 170° C., 140° C. or 100° C. in accordance with JIS K6300.

[0112] The above-mentioned partially fluorinated elastomers and perfluoroelastomers can be produced by conventional methods, but iodine or bromine compounds can also be used as chain transfer agents because the molecular weight distribution of the resulting polymer is narrow, molecular weight control is easy, and iodine or bromine atoms can be introduced to the ends. Polymerization methods using iodine or bromine compounds include, for example, a method in which emulsion polymerization is carried out in an aqueous medium under pressure in the presence of an iodine or bromine compound in a substantially oxygen-free state (iodine transfer polymerization method). Representative examples of iodine or bromine compounds that can be used include, for example, compounds represented by the general formula: R 21 I x Br y (In the formula, x and y are each an integer of 0 to 2, and 1≦x+y≦2 is satisfied; R 21is a saturated or unsaturated fluorohydrocarbon group or chlorofluorohydrocarbon group having 1 to 16 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom). By using an iodine compound or a bromine compound, an iodine atom or a bromine atom is introduced into the polymer and functions as a crosslinking point.

[0113] Examples of iodine compounds and bromine compounds include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo-n-propane, CF2Br2, BrCF2CF2Br, CF3CFBrCF2Br, CFClBr2, BrCF Examples of the iodoperfluoroalkyl group include 2CFClBr, CFBrClCFClBr, BrCF2CF2CF2Br, BrCF2CFBrOCF3, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodomonobromo-substituted benzene, diiodomonobromo-substituted benzene, and (2-iodoethyl) and (2-bromoethyl)-substituted benzene. These compounds may be used alone or in combination with each other.

[0114] Among these, it is preferable to use 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane in terms of polymerization reactivity, crosslinking reactivity, availability, and the like.

[0115] The fluorine-containing elastomer preferably has a cyano group (-CN group). The fluorine-containing elastomer having a cyano group (-CN group) can be crosslinked by forming a triazine ring through cyclotrimerization of the cyano group, and can impart excellent compression set properties and heat resistance to the crosslinked product.

[0116] The above-mentioned fluorine-containing elastomer having a cyano group preferably has a cyano group (-CN group) at the main chain terminal and / or at a side chain.

[0117] Examples of fluorine-containing elastomers having a cyano group (-CN group) at the main chain end and / or in the side chain include perfluoroelastomers and partially fluorinated elastomers.

[0118] The perfluoroelastomer having a cyano group (-CN group) at the main chain end and / or side chain may be the above-mentioned TFE / fluoromonomer represented by general formula (13), (14) or (15) / monomer copolymer that provides a crosslinking site, in which the monomer that provides the crosslinking site is a monomer having a cyano group (-CN group). In this case, the content of the monomer unit having a cyano group (-CN group) may be 0.1 to 5 mol % or 0.3 to 3 mol % based on the total amount of the TFE unit and the fluoromonomer unit represented by general formula (13), (14) or (15) from the viewpoint of good crosslinking properties and heat resistance. More preferable compositions are as described above.

[0119] Examples of monomers having a cyano group (-CN group) include: Formula:CY 1 2=CY 1 (CF2) n -CN (In the formula, Y 1 are each independently a hydrogen atom or a fluorine atom, and n is an integer of 1 to 8. Formula: CF2=CFCF2Rf 8 -CN (In the formula, Rf 8 Ha-(OCF2) n-or-(OCF(CF3)) n -, and n is an integer from 0 to 5. Formula: CF2 = CFCF2(OCF(CF3)CF2) m (OCH2CF2CF2) n OCH2CF2-CN (In the formula, m is an integer of 0 to 5, and n is an integer of 0 to 5.) Formula: CF2=CFCF2(OCH2CF2CF2) m (OCF(CF3)CF2) n OCF(CF3)-CN (In the formula, m is an integer of 0 to 5, and n is an integer of 0 to 5.) Formula: CF2 = CF(OCF2CF(CF3)) m O(CF2) n -CN (In the formula, m is an integer of 0 to 5, and n is an integer of 1 to 8.) Formula: CF2 = CF(OCF2CF(CF3)) m -CN (In the formula, m is an integer of 1 to 5). Formula: CF2 = CFOCF2(CF(CF3)OCF2) n CF(-CN)CF3 (wherein n is an integer of 1 to 4). Formula: CF2 = CFO(CF2) n OCF(CF3)-CN (wherein n is an integer of 2 to 5). Formula: CF2 = CFO(CF2) n -(C6H4)-CN (wherein n is an integer of 1 to 6). Formula: CF2 = CF(OCF2CF(CF3)) n OCF2CF(CF3)-CN (wherein n is an integer of 1 to 2). Formula: CH2=CFCF2O(CF(CF3)CF2O) n CF(CF3)-CN (wherein n is an integer of 0 to 5), Formula: CF2 = CFO(CF2CF(CF3)O) m (CF2) n -CN (In the formula, m is an integer of 0 to 5, and n is an integer of 1 to 3.) Formula: CH2=CFCF2OCF(CF3)OCF(CF3)-CN Formula:CH2=CFCF2OCH2CF2-CN Formula: CF2 = CFO(CF2CF(CF3)O) m CF2CF(CF3)-CN (wherein m is an integer of 0 or more) Formula: CF2 = CFOCF(CF3)CF2O(CF2) n -CN (wherein n is an integer of 1 or more) Formula: CF2=CFOCF2OCF2CF(CF3)OCF2-CN These can be used alone or in any combination.

[0120] Among the above, Formula: CF2 = CF(OCF2CF(CF3)) m O(CF2) n -CN (wherein m is an integer of 0 to 5, and n is an integer of 1 to 8), and CF2=CFOCF2CF(CF3)OCF2CF2CN is more preferred.

[0121] These perfluoroelastomers can be produced by conventional methods.

[0122] Specific examples of such perfluoroelastomers include fluororubbers described in International Publication No. 97 / 24381, JP-B-61-57324, JP-B-4-81608, and JP-B-5-13961.

[0123] Examples of partially fluorinated elastomers having a cyano group (-CN group) at the main chain end and / or side chain include vinylidene fluoride (VdF)-based fluororubber, tetrafluoroethylene (TFE) / propylene-based fluororubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF)-based fluororubber, ethylene / hexafluoroethylene (HFP)-based fluororubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF)-based fluororubber, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE)-based fluororubber, fluorosilicone-based fluororubber, and fluorophosphazene-based fluororubber, which may be used alone or in any combination within the scope that does not impair the effects of the present disclosure.

[0124] The vinylidene fluoride-based fluororubber refers to a fluorocopolymer consisting of 45-85 mol% vinylidene fluoride and 55-15 mol% of at least one other monomer copolymerizable with vinylidene fluoride, preferably 50-80 mol% vinylidene fluoride and 50-20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.

[0125] Examples of at least one other monomer copolymerizable with vinylidene fluoride include fluoromonomers such as TFE, CTFE, trifluoroethylene, HFP, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, perfluoro(alkyl vinyl ether) (PAVE), and vinyl fluoride, and non-fluorinated monomers such as ethylene, propylene, and alkyl vinyl ether. These can be used alone or in any combination. Among these, TFE, HFP, and perfluoro(alkyl vinyl ether) are preferred.

[0126] Specific examples of rubber include VdF-HFP rubber, VdF-HFP-TFE rubber, VdF-CTFE rubber, and VdF-CTFE-TFE rubber.

[0127] These partially fluorinated elastomers can be produced by conventional methods.

[0128] As the fluorine-containing elastomer, a thermoplastic fluorine-containing rubber comprising an elastomeric fluorine-containing polymer chain segment and a non-elastomeric fluorine-containing polymer chain segment may also be used.

[0129] The content of the fluoropolymer (P) in the composition of the present disclosure is preferably 0.5 to 100 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, based on 100 parts by mass of the polymer (E). When the polymer (E) is a fluorine-containing elastomer, the content of the fluoropolymer (P) in the composition of the present disclosure is preferably 0.5 to 100 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, based on 100 parts by mass of the fluorine-containing elastomer.

[0130] <Other ingredients> The composition of the present disclosure may further contain a filler (with the exception of the fluoropolymer (P)).

[0131] Examples of the filler include imide-based fillers having an imide structure, such as polyimide, polyamideimide, and polyetherimide; organic fillers made of engineering plastics, such as polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyetherketone, and polyoxybenzoate; metal oxide fillers, such as silicon oxide, aluminum oxide, and yttrium oxide; metal carbides, such as silicon carbide and aluminum carbide; metal nitride fillers, such as silicon nitride and aluminum nitride; and inorganic fillers, such as carbon black, aluminum fluoride, and carbon fluoride.

[0132] Among these, carbon black, aluminum oxide, silicon oxide, yttrium oxide, silicon carbide, silicon nitride, polyimide, and carbon fluoride are preferred from the viewpoint of shielding effect against various plasmas.

[0133] The inorganic fillers and organic fillers may be used alone or in combination of two or more kinds.

[0134] The content of the filler is preferably 0.01 to 100 parts by mass, more preferably 0.05 to 50 parts by mass, further preferably 0.05 to 10 parts by mass, and particularly preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the polymer (E).

[0135] In particular, in fields where high purity and non-staining properties are not required, ordinary additives that are blended into compositions, such as processing aids, plasticizers, colorants, etc., may be blended as necessary, and one or more commonly used crosslinking agents or crosslinking assistants different from those described above may also be blended.

[0136] The composition may contain an organic basic compound. The organic basic compound may be a compound represented by the formula: CH3(CH2) 17 -Octadecylamine in NH2; Formula:H2N-C(O)-(CH2) 11 -CH=CH-(CH2)7CH3 erucamide; Oleamide of formula: H2N-C(O)-(CH2)7-CH=CH-(CH2)7CH3; Hexamethylenediamine of formula H2N-(CH2)6-NH2 formula: [ka] Examples of such aryl ethers include 1,8-diazabicycloundec-7-ene (DBU).

[0137] The composition of the present disclosure preferably further contains at least one selected from the group consisting of inorganic nitrides, organic tin compounds, compounds that generate ammonia, and crosslinking agents. In particular, when the polymer (E) is an elastomer, it is preferable to use these. When the composition of the present disclosure contains these components such as a crosslinking agent, a crosslinked product can be easily obtained from the composition of the present disclosure. In the following, a preferred configuration of the composition when the polymer (E) is a fluorine-containing elastomer will be described.

[0138] The inorganic nitride is not particularly limited, but examples thereof include silicon nitride (Si3N4), lithium nitride, titanium nitride, aluminum nitride, boron nitride, vanadium nitride, zirconium nitride, etc. Among these, silicon nitride is preferable because nano-sized fine particles can be supplied.

[0139] Examples of the organotin compounds include tetraphenyltin and triphenyltin.

[0140] As the compound that generates ammonia, a compound that generates ammonia at 40 to 330°C is preferable.

[0141] The ammonia-generating compound is preferably urea or its derivatives, or an ammonium salt, more preferably urea or an ammonium salt, and even more preferably urea. The ammonium salt may be an organic ammonium salt or an inorganic ammonium salt. The ammonia-generating compound may also be one that reacts with a small amount of water to generate ammonia.

[0142] Examples of urea derivatives include biurea, thiourea, urea hydrochloride, and biuret.

[0143] Examples of the organic ammonium salt include compounds described in JP-A-9-111081, WO-A-00 / 09603, and WO-A-98 / 23675, such as ammonium salts of polyfluorocarboxylic acids such as ammonium perfluorohexanoate and ammonium perfluorooctanoate; ammonium salts of polyfluorosulfonic acids such as ammonium perfluorohexane sulfonate and ammonium perfluorooctane sulfonate; ammonium salts of polyfluoroalkyl group-containing phosphoric or phosphonic acids such as ammonium perfluorohexane phosphate and ammonium perfluorooctane phosphate; and ammonium salts of non-fluorinated carboxylic or sulfonic acids such as ammonium benzoate, ammonium adipate, and ammonium phthalate.

[0144] Examples of inorganic ammonium salts include the compounds described in JP-A-9-111081, such as ammonium sulfate, ammonium carbonate, ammonium nitrate, and ammonium phosphate.

[0145] Further, examples of the ammonia generating compound include acetaldehyde ammonia, hexamethylenetetramine, formamidine, formamidine hydrochloride, formamidine acetate, t-butyl carbamate, benzyl carbamate, HCF2CF2CH(CH3)OCONH2, and phthalamide.

[0146] Examples of the crosslinking agent include crosslinking agents used in peroxide crosslinking, polyol crosslinking, polyamine crosslinking, triazine crosslinking, oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking. When the fluorine-containing elastomer is a fluorine-containing elastomer having a cyano group (-CN group), the crosslinking agent is preferably at least one selected from the group consisting of an oxazole crosslinking agent, an imidazole crosslinking agent, and a thiazole crosslinking agent.

[0147] The crosslinking agent used in the peroxide crosslinking may be any organic peroxide that can easily generate peroxy radicals in the presence of heat or an oxidation-reduction system. Specific examples of the crosslinking agent include 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide (Perbutyl D), t-butylcumyl peroxide (Perbutyl C), dicumyl peroxide (Percumyl D, Percumyl D-40, Percumyl D-40MB(T)), α,α- Bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B, Perhexa 25B-40), 2,5-dimethyl-2,5-di(t-butylperoxy)-hexyne-3 (Perhexyne 25B, Perhexyne 25B-40), benzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane (Perhexa 25Z), t-butylperoxymaleic acid (t-butyl MA), t-butyl Chilperoxy isopropyl carbonate (Perbutyl I-75), methyl ethyl ketone peroxide (Permec D (DR), Permec H (HR, HY), Permec N (NR, NY), Permec S (SR), Permec F (FR), Permec G (GR, GY)), cyclohexanone peroxide (Perhexa H), acetylacetone peroxide (Percure AH, AL), 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane (Perhexa TMH), 1,1-di(t-hexyl Peroxy)cyclohexane (Perhexa HC), 1,1-di(t-butylperoxy)-2-methylcyclohexane (Perhexa MC), 1,1-di(t-butylperoxy)cyclohexane (Perhexa C-80(S), Perhexa C-75(EB), Perhexa C(C), Perhexa C-40, Perhexa C-40MB(S)), 2,2-di(t-butylperoxy)butane (Perhexa 22), 4,4-di-(t-butylperoxy)butylpentanoate (Perhexa V, Perhexa V-40(F)), 2,2-di(4,4-Di-(t-butylperoxy)cyclohexyl)propane (Pertetra A), p-menthane hydroperoxide (Permenta H), diisopropylbenzene hydroperoxide (Percumyl P), 1,1,3,3-tetramethylbutyl hydroperoxide (Perocta H), cumene hydroperoxide (Percumyl H-80), t-butyl hydroperoxide (Perbutyl H-69), di(2-t-butylperoxyisopropanol) Perbutyl P, Perbutyl P-40, Peroximon F-40, Perbutyl P-40MB(K)), Di-t-hexyl peroxide (Perhexyl D), Diisobutyryl peroxide (Peroyl IB), Di(3,5,5-trimethylhexanoyl) peroxide (Peroyl 355(S)), Dilauroyl peroxide (Peroyl L), Disuccinic acid peroxide (Peroyl SA), Di-(3-methylbenzoyl) peroxide (Peroyl 1H), Diisobutyryl peroxide (Peroyl 2H), Diisobutyryl peroxide (Peroyl 1 ... Benzoyl (3-methylbenzoyl) peroxide and dibenzoyl peroxide mixture (Niper BMT-K40, Niper BMT-M), dibenzoyl peroxide (Niper BW, Niper BO, Niper FF, Niper BS, Niper E, Niper NS), di(4-methylbenzoyl) peroxide (Niper PMB), di-n-propyl peroxydicarbonate (Peroyl NPP-50M ), diisopropyl peroxydicarbonate (Perloyl IPP-50, Perloyl IPP-27), di(4-t-butylcyclohexyl) peroxydicarbonate (Perloyl TCP), di(2-ethylhexyl) peroxydicarbonate (Perloyl OPP), di-sec-butyl peroxydicarbonate (Perloyl SBP), cumyl peroxyneodecanoate (Perloyl ND, Perloyl ND-50E), 1,1,3,3-Tetramethylbutyl peroxyneodecanoate (Perocta ND, Perocta ND-50E), t-hexyl peroxyneodecanoate (Perhexyl ND, Perhexyl ND-50E), t-butyl peroxyneodecanoate (Perbutyl ND, Perbutyl ND-50E), t-butyl peroxyneoheptanoate (Perbutyl NHP), t-hexyl peroxypivalate (Perhexyl PV, Perhexyl PV-50E), t -Butyl peroxypivalate (Perbutyl PV, Perbutyl PV-40E), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O), 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane (Perhexa 25 O), t-hexylperoxy-2-ethylhexanoate (Perhexyl O, Percure HO(N)), t-butylperoxy-2-ethylhexanoate (Perb Chil O, Percure O), t-hexylperoxyisopropyl monocarbonate (Perhexyl I), t-butylperoxy-3,5,5-trimethylhexanoate (Perbutyl 355), t-butylperoxylaurate (Perbutyl L), t-butylperoxy-2-ethylhexyl monocarbonate (Perbutyl E), t-hexylperoxybenzoate (Perhexyl Z), t-butylperoxyacetate (Perbutyl A), Examples include a mixture of t-butylperoxy-3-methylbenzoate and t-butylperoxybenzoate (Perbutyl ZT), t-butylperoxybenzoate (Perbutyl Z), t-butylperoxyallyl monocarbonate (Peromer AC), 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone (BTTB-25), and 2,3-dimethyl-2,3-diphenylbutane (Nofumer BC-90). Among these, dialkyl types are preferred. Furthermore, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane is particularly preferred. In general, the type and amount of organic peroxide used are selected taking into consideration the amount of active -OO-, decomposition temperature, etc.

[0148] In addition, the crosslinking auxiliary that can be used in this case may be any compound that has a reactive activity against peroxy radicals and polymer radicals, such as polyfunctional compounds having functional groups such as -CH=CH2, -CH2CH=CH2, -CF=CF2, -C(CF3)=CF2, -C(CH3)=CF2, -CF=CF(CF3), -CF=CF(CH3), -C(C6H5)=CF2, -CF=CF(C6H5), -CH=CF2, -CF=CHF, -C(CF3)=CHF, -CF=CH(CF3), and -CH=CF(CF3) ("C6H5" in each formula represents a phenyl group). Specific examples include triallyl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N,N'-n-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris(2,3,3-trifluoro-2-propenyl)-1,3,5-triazine 2,4,6-trione), tris(diallylamine)-S-triazine, triallyl phosphite, N,N-diallylacrylamide, and 1,6-divinyldodecafluorohexane.

[0149] In addition, the crosslinking aid used together with the peroxide crosslinking agent is represented by the general formula (31): [ka] (Wherein, six R 31 are each independently H, a halogen atom, or an optionally halogenated group having 1 to 5 carbon atoms which may have an ether bond inserted therein; Z 31 can also include a compound represented by a linear or branched alkylene group, cycloalkylene group, or (per)fluoropolyoxyalkylene group having 1 to 18 carbon atoms, which optionally contains a heteroatom and is optionally halogenated.

[0150] The compound represented by the general formula (31) includes the compound represented by the general formula (32): [ka] (In the formula, j is an integer of 2 to 10, preferably an integer of 4 to 8, and four R 32 each independently represents H, F, or an alkyl group or a (per)fluoroalkyl group having 1 to 5 carbon atoms), [ka] (In the formula, Y 31 are each independently F, Cl or H; Y 32 each independently represents F, Cl, H, or OR 33 (where R 33 is a branched or straight chain alkyl group, which may be partially, substantially or completely fluorinated or chlorinated; Z 33 is a divalent group having 2 to 10 carbon atoms, optionally fluorinated, which may have an ether bond inserted therein, preferably Z 33 m is an integer from 3 to 5; -(CF2) m - group, and the compound represented by general formula (33) is preferably F2C=CF-O-(CF2)5-O-CF=CF2), a compound represented by general formula (34): [ka] (In the formula, Y 31 , Y 32 and Z 33 is as above, and R 34 are each independently H, F, or an alkyl group or a (per)fluoroalkyl group having 1 to 5 carbon atoms.

[0151] The crosslinking agent or the crosslinking assistant used together with the peroxide crosslinking agent may be a crosslinking agent represented by the general formula (35): [ka]

[0152] (In the formula, R 35 ~R 37 are each independently a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, or a substituted or unsubstituted aryl group; R 35 ~R 37 At least one of R is a fluorine atom or a group containing a fluorine atom. m is an integer of 1 to 5. When m is 2 or more, m R 35 ~R 37 may be the same or different. The hydrogen atom of the benzene ring may be substituted. When m is 1, it is preferable that the compound has two or more of the structure.

[0153] The compound having a structure represented by general formula (36) includes compounds represented by general formula (36): [ka]

[0154] (In the formula, R 35 ~R 37 is as defined above, p is an integer of 0 to 2, and n is an integer of 2 to 6.), a compound represented by the general formula (37): [ka]

[0155] (In the formula, R 35 ~R 37 As stated above. R 38 is 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 of 1 to 5. These groups may be partially or completely fluorinated.

[0156] The heteroatom-containing group is not particularly limited as long as it is a divalent group containing a heteroatom. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, a boron atom, and a phosphorus atom.

[0157] Examples of crosslinking agents used in polyol crosslinking include polyhydric alcohol compounds such as bisphenol A and bisphenol AF.

[0158] Examples of crosslinking agents used in polyamine crosslinking include polyamine compounds such as hexamethylenediamine carbamate, N,N'-dicinnamylidene-1,6-hexanediamine, and 4,4'-bis(aminocyclohexyl)methane carbamate.

[0159] Examples of the crosslinking agent used for the oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking include those represented by the general formula (41):

[0160] [ka]

[0161] (In the formula, R 41 is -SO2-, -O-, -CO-, an alkylene group having 1 to 6 carbon atoms, a perfluoroalkylene group having 1 to 10 carbon atoms or a single bond, or

[0162] [ka]

[0163] R 42 and R 43 One is -NH2 and the other is -NHR 44 , -NH2, -OH or -SH, and R 44 is a hydrogen atom, a fluorine atom or a monovalent organic group, preferably R 42 is -NH2 and R 43 Ga-NHR 44Preferred specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, and examples of the perfluoroalkylene group having 1 to 10 carbon atoms include

[0164] [ka]

[0165] These compounds are known as examples of bisdiaminophenyl compounds in JP-B-2-59177, JP-A-8-120146, etc.) and include bisdiaminophenyl crosslinking agents, bisaminophenol crosslinking agents, bisaminothiophenol crosslinking agents, and crosslinking agents represented by the general formula (42):

[0166] [ka] (R 41 As mentioned above, R 45 are each independently any of the following groups: [ka]

[0167] Bisamidrazone crosslinking agents represented by general formula (43):

[0168] [ka]

[0169] (In the formula, Rf 41 is a perfluoroalkylene group having 1 to 10 carbon atoms), or an amidrazone crosslinking agent represented by the general formula (44):

[0170] [ka]

[0171] (wherein n is an integer of 1 to 10), a bisamidoxime-based crosslinking agent represented by the general formula (45): HN=CR 45 R 46 (In the formula, R 45 are H, NH2, and NHR 47 R 46 Ph, SO2H, NR 48 R 49 , 2-pyridine, and CH2CONH2; R 47 is selected from the group consisting of Ph, NH2, and CN; R 48 is selected from the group consisting of H, NHPh, CH2CONH2, a linear alkyl group having 1 to 8 carbon atoms, and a branched alkyl group having 1 to 8 carbon atoms, and R 49 Ph, COOC(CH3)3, NH2, CH2COOH, CSNH2, CNHNH3 + Cl - , p-phenylCN, [ka] and COPh). These bisaminophenol-based crosslinking agents, bisaminothiophenol-based crosslinking agents, and bisdiaminophenyl-based crosslinking agents have been used in the past in crosslinking systems that use cyano groups as crosslinking points, but they also react with carboxyl groups and alkoxycarbonyl groups to form oxazole rings, thiazole rings, and imidazole rings, resulting in crosslinked products.

[0172] In addition, the crosslinking agent may be a compound represented by the general formula (46): X 41 -(CH2) n -R 50 -(CH2) m -X 41 (In the formula, X 41 each independently represents an alkyne group, a nitrile group, or Y 41 P N3(Y 41 is SO, SO2, C6H4 or CO, and p is 0 or 1), n ​​and m are independently integers of 1 to 4, R 50teeth, i) a fluoroalkylene group having 3 to 10 carbon atoms, ii) a fluoroalkoxysilane group having 3 to 10 carbon atoms, iii) a substituted arylene group, iv) oligomers containing copolymerized units of vinylidene fluoride and perfluoro(methyl vinyl ether); v) oligomers containing copolymerized units of vinylidene fluoride and hexafluoropropylene; vi) oligomers containing copolymerized units of tetrafluoroethylene and perfluoro(methyl vinyl ether); and vii) a crosslinking agent selected from the group consisting of oligomers containing copolymerized units of tetrafluoroethylene and hydrocarbon olefin. This crosslinking agent is preferably used together with a fluorine-containing elastomer having a nitrile group, an azide group, a sulfonyl azide group, a carbonyl azide group or an alkyne group. For example, the nitrile group of the fluorine-containing elastomer reacts with the azide group of the crosslinking agent to form a tetrazole ring, giving a crosslinked product.

[0173] Particularly preferred crosslinking agents include compounds having multiple 3-amino-4-hydroxyphenyl groups or 3-amino-4-mercaptophenyl groups, or compounds represented by the general formula (47):

[0174] [ka]

[0175] (In the formula, R 41 , R 42 and R 43As described above, specific examples of the compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (general 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)phenyl] [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, and the like.

[0176] Among these, the crosslinking agent is preferably 2,2-bis[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane in terms of heat resistance, steam resistance, amine resistance, and good crosslinking properties.

[0177] The content of at least one selected from the group consisting of inorganic nitrides, organotin compounds, compounds that generate ammonia, and crosslinking agents is preferably 0.05 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the fluorine-containing elastomer.

[0178] The composition can be prepared by mixing the above components using a typical polymer processing machine such as an open roll, a Banbury mixer, a kneader, etc. Alternatively, it can be prepared by a method using an internal mixer. The composition can be suitably used as a molding material for obtaining a crosslinked product by crosslinking molding.

[0179] Also, fluoropolymer (P) and fluorine-containing elastomer are co-precipitated in aqueous medium to prepare the composition containing fluoropolymer (P) and fluorine-containing elastomer, and then, optionally, other components are added to the composition to prepare the composition.

[0180] The crosslinked product of the present disclosure is obtained from the above composition. The crosslinked product of the present disclosure has excellent plasma resistance and has small compression set even when used under harsh conditions. The crosslinked product of the present disclosure is preferably a crosslinked product obtained by crosslinking the above composition, since it has even better plasma resistance and compression set properties.

[0181] A method for obtaining a crosslinked product from the composition includes a method in which a preform is obtained using the composition as a molding material, and then the preform is crosslinked. A method for obtaining a preform using the composition as a molding material may be a conventional method, and may be a known method such as a method of heating and compressing in a mold, a method of pressing into a heated mold, or a method of extruding with an extruder. In the case of extrusion products such as hoses and electric wires, a crosslinked product can be obtained by performing heat crosslinking with steam or the like after extrusion.

[0182] The crosslinking can be carried out in the order of primary crosslinking and secondary crosslinking. The primary crosslinking is preferably carried out at 150 to 200° C. for 5 to 120 minutes, and more preferably at 170 to 190° C. for 5 to 60 minutes. As the crosslinking means, a known crosslinking means may be used, and an example of the crosslinking means includes press crosslinking.

[0183] The secondary crosslinking is preferably carried out at 180 to 320° C. for 2 to 24 hours, more preferably at 200 to 310° C. for 5 to 20 hours. The temperature may be changed within this temperature range. As the crosslinking means, a known crosslinking means may be used, for example, oven crosslinking.

[0184] The crosslinked product of the present disclosure can be suitably used as a sealing material for semiconductor manufacturing equipment that requires heat resistance, particularly for semiconductor manufacturing equipment that is exposed to high-density plasma. Examples of the sealing material include O-rings, square rings, gaskets, packing, oil seals, bearing seals, and lip seals. In addition, it can be used for various polymer products used in semiconductor manufacturing equipment, such as diaphragms, tubes, hoses, various rubber rolls, belts, etc. It can also be used as a coating material or a lining material.

[0185] It should be noted that the semiconductor manufacturing equipment referred to in this disclosure is not limited to equipment specifically for manufacturing semiconductors, but broadly includes all manufacturing equipment used in the semiconductor field that requires a high degree of cleanliness, such as equipment for manufacturing liquid crystal panels and plasma panels, and examples of such equipment include the following:

[0186] (1) Etching equipment Dry Etching Equipment Plasma Etching Equipment Reactive Ion Etching Equipment Reactive Ion Beam Etching Equipment Sputter Etching Equipment Ion Beam Etching Equipment Wet Etching Equipment Ashing device (2) Cleaning equipment: Dry etching cleaning equipment UV / O3 cleaning equipment Ion Beam Cleaning Equipment Laser Beam Cleaning Equipment Plasma Cleaning Equipment Gas Etching Cleaning Equipment Extraction and Cleaning Equipment Soxhlet Extraction and Cleaning Apparatus High-temperature and high-pressure extraction and cleaning equipment Microwave Extraction Cleaning Equipment Supercritical Extraction Cleaning Equipment (3) Exposure equipment Stepper Coater Developer (4) Polishing equipment CMP equipment (5) Film deposition equipment CVD equipment Sputtering Equipment (6) Diffusion and ion implantation equipment Oxidation Diffusion Device Ion implantation equipment

[0187] The crosslinked product of the present disclosure exhibits excellent performance as a sealing material for, for example, a CVD apparatus, a plasma etching apparatus, a reactive ion etching apparatus, an ashing apparatus, or an excimer laser exposure apparatus.

[0188] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0189] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to these examples.

[0190] The values ​​in the examples were measured by the following methods.

[0191] <Solid content concentration> 1 g of the aqueous dispersion was dried in a blower dryer at 150° C. for 60 minutes, and the ratio of the mass of the heating residue to the mass (1 g) of the aqueous dispersion was expressed as a percentage and used.

[0192] <Average primary particle diameter> The average primary particle diameter was determined by determining the correlation between the transmittance when 550 nm light was incident on a specified cell into which a fluoropolymer aqueous dispersion adjusted to a solid content of 0.15 mass% was poured, and the number average primary particle diameter calculated by measuring the unidirectional diameter using a transmission electron microscope photograph, and then applying the transmittance measured for the obtained sample to the above correlation (calibration curve method).

[0193] <Infrared absorption spectrum analysis> Infrared absorption spectrum analysis was performed using a Fourier transform infrared spectrometer to obtain the infrared absorption spectrum of the fluoropolymer powder obtained by coagulation and drying. The height ratio of each peak appearing in the obtained absorption spectrum was calculated by the following method. Spectral intensity ratio 1=h1 / h0 Spectral intensity ratio 2=h2 / h0 h0: CF overtones (2360-2370cm -1 ) peak height h1: Stretching vibration of branched chain (1030-1040cm -1 ) peak height h2: C=C stretching (1780~1800cm -1 ) peak height

[0194] <Perfluoroalkadiene unit content> 19 The results were measured by F-NMR analysis.

[0195] <Peak temperature> Approximately 10 mg of fluoropolymer powder that had not been heated to temperatures above 300°C was precisely weighed, placed in a dedicated aluminum pan, and measured using a TG / DTA (thermogravimetric / differential thermal analyzer). The peak temperature was determined as the temperature corresponding to the maximum value on a differential thermal (DTA) curve obtained by heating the aluminum pan in an air atmosphere over the temperature range of 25°C to 600°C at a rate of 10°C / min.

[0196] <Deformation ratio> 1.7 g of PTFE powder was filled into a cylindrical mold with a diameter of 13 mm at room temperature. Next, the pressure was gradually increased to 29.4 MPa and held for 5 minutes, after which the mold was removed to obtain a preform. This preform was placed in an air circulating furnace at 40°C, heated to 370°C at a heating rate of 25°C / hour, sintered at 370°C for 90 minutes, cooled to 40°C at a cooling rate of 25°C / hour, removed from the furnace and slowly cooled to room temperature. A cylindrical compression test piece with a diameter of 13.0 mm and a height of 5.85 mm was cut out from the obtained molded body.

[0197] The obtained test piece and compression jig were preheated to 200°C. It was compressed at 200°C to a compression ratio of 30% (a test piece with a height of 5.85 mm was compressed to a height of 4.095 mm). After compression at 200°C for 24 hours, the test piece was removed from the compression jig and allowed to stand at 23°C for 30 minutes, and the height (t1) of the test piece was measured. The deformation ratio was calculated using the following formula. A small deformation ratio means excellent creep resistance. Deformation rate (%) = (t0-t1) / t0 x 100 t0: Height of the test piece before the test (mm) t1: Height of the test piece after compression test (mm) In the above test, t0=5.85 mm.

[0198] <Melt viscosity> According to ASTM D 1238, a flow tester (manufactured by Shimadzu Corporation) and a 2φ-8L die were used to measure a 2g sample that had been preheated at 380°C for 5 minutes under a load of 0.7 MPa while maintaining the temperature at the above temperature. Since none of the fluoropolymers obtained in Synthesis Examples 1 to 4 melted, the melt viscosity could not be measured.

[0199] <Standard specific gravity (SSG)> The measurement was performed by the water displacement method according to ASTM D 792 using samples molded according to ASTM D4895-89.

[0200] Synthesis Example 1 (Production of Fluoropolymer) A 0.3 L stirred glass reactor was charged with 150 g of deionized water, 6 g of paraffin wax, and 0.225 g of 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(trifluoromethoxy)propoxy]-propanoic acid ammonium salt dispersant (CF3OCF(CF3)CF2OCF(CF3)COONH4) [PMPA]. The reactor contents were then heated to 70°C to deoxygenate. Perfluorooctadiene (CF2=CF(CF2)4CF=CF2) was added in the amount listed in Table 1, and then 0.015 g of ammonium persulfate (APS) initiator dissolved in 2 g of deionized water was injected into the reactor, bringing the reactor to a pressure of 0.835 MPaG. After the injection of the initiator, a drop in pressure occurred and the initiation of polymerization was observed. TFE was added to the reactor to maintain the pressure, and polymerization was continued until about 40 g of TFE had reacted. After that, the pressure in the reactor was vented to normal pressure, and the contents were removed from the reactor and cooled. The supernatant paraffin wax was removed from the fluoropolymer aqueous dispersion. The solids concentration of the obtained aqueous dispersion and the average primary particle size of the primary particles in the aqueous dispersion are shown in Table 1.

[0201] The obtained aqueous dispersion was diluted with deionized water to a solid content of about 15% by mass, and 2.5 g of nitric acid was added to 100 g of the obtained aqueous fluoropolymer dispersion and coagulated by stirring. The obtained wet powder was filtered and washed with 3000 g of deionized water. After repeating this washing operation three times, the powder was dried in a heat circulation dryer at 150°C for 18 hours to obtain a fluoropolymer powder. The results are shown in Table 1.

[0202] Synthesis Examples 2 to 4 (Production of Fluoropolymers) A fluoropolymer aqueous dispersion and a fluoropolymer powder were obtained in the same manner as in Synthesis Example 1, except that the amount of perfluorooctadiene added was changed as shown in Table 1. The results are shown in Table 1.

[0203] Synthesis Example 5 (Production of Fluoropolymer) A 0.3 L stirred glass reactor was charged with 150 g deionized water, 6 g paraffin wax, and 0.225 g 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(trifluoromethoxy)propoxy]-propanoic acid ammonium salt dispersant (CF3OCF(CF3)CF2OCF(CF3)COONH4) [PMPA]. The reactor contents were then heated to 70°C to deoxygenate. 4 mg propane gas and 0.16 g perfluorooctadiene (CF2=CF(CF2)4CF=CF2) were then added, followed by injection of 0.015 g ammonium persulfate (APS) initiator in 2 g deionized water, which brought the reactor to a pressure of 0.835 MPaG. After the injection of the initiator, a drop in pressure occurred and the initiation of polymerization was observed. TFE was added to the reactor to maintain the pressure, and polymerization was continued until about 40 g of TFE had reacted. After that, the pressure in the reactor was vented to normal pressure, and the contents were removed from the reactor and cooled. The supernatant paraffin wax was removed from the aqueous fluoropolymer dispersion.

[0204] The obtained aqueous dispersion was diluted with deionized water to a solid content of about 20% by mass, and 2.5 g of nitric acid was added to 100 g of the obtained aqueous fluoropolymer dispersion and coagulated by stirring. The obtained wet powder was filtered and washed with 3000 g of deionized water. After repeating this washing operation three times, the powder was dried in a heat circulation dryer at 150°C for 18 hours to obtain a fluoropolymer powder. The results are shown in Table 3.

[0205] Synthesis Example 6 (Production of Fluoropolymer) A fluoropolymer aqueous dispersion and a fluoropolymer powder were obtained in the same manner as in Synthesis Example 5, except that the amount of propane gas was changed from 4 mg to 2 mg in Synthesis Example 5. The results are shown in Table 3.

[0206] Comparative Synthesis Example 1 (Production of Fluoropolymer) Except for not adding perfluorooctadiene, an aqueous fluoropolymer dispersion and a fluoropolymer powder were obtained in the same manner as in Synthesis Example 1. The results are shown in Table 1.

[0207] Comparative synthesis example 2 A fluoropolymer aqueous dispersion and a fluoropolymer powder were obtained in the same manner as in Synthesis Example 1, except that perfluorooctadiene was replaced with perfluoro[3-(1-methyl-2-vinyloxy-ethoxy)propionitrile] (hereinafter abbreviated as CNVE) and the drying conditions were changed to 24 hours in a vacuum drying oven at 70° C. The results are shown in Table 1.

[0208] Comparative synthesis example 3 Except for not adding perfluorooctadiene, the same procedure as in Synthesis Example 5 was carried out to obtain an aqueous fluoropolymer dispersion and a fluoropolymer powder. The results are shown in Table 3.

[0209] [Table 1]

[0210] Next, examples in which the above-produced fluoropolymer was used as a filler will be described. The various values ​​in the examples were measured by the following methods.

[0211] <Composition of Fluorine-Containing Elastomer> 19 The results were measured by F-NMR and IR analysis.

[0212] <Mooney viscosity> Measurement was performed at 170° C. in accordance with JIS K6300 using a Mooney viscometer MV2000E manufactured by ALPHA TECHNOLOGIES.

[0213] <Crosslinking properties> Using RPA2000 manufactured by ALPHA TECHNOLOGIES, the crosslinking curve of the obtained composition was obtained 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.

[0214] <Compression set> The compression set was measured in accordance with the methods described in ASTM D395 or JIS K6262. The O-rings prepared in the examples and comparative examples were compressed to a compression ratio of 25% at room temperature (the O-ring with a thickness (wire diameter) of 3.5 mm was compressed to a thickness of 2.625 mm) using a compression device. Next, the compression device with the compressed O-ring fixed was placed still in an electric furnace, left for 70 hours at 200 °C, and then the compression device was taken out of the electric furnace. After that, the compression device with the compressed O-ring fixed was placed still in another electric furnace and left for 24 hours at 70 °C. The O-ring was removed from the compression device, and the removed O-ring was placed still in a constant temperature chamber and left for 30 minutes at 23 °C, and the thickness (t2) of the O-ring was measured. The compression set was determined by the following formula. A small compression set means excellent recoverability at low temperature after use at high temperature, and means excellent performance under conditions close to the O-ring usage environment. Compression set (%) = (t0 - t2) / (t0 - t1) × 100 t0: Original thickness of the O-ring (mm) t1: Thickness of the spacer (mm) t2: Thickness of the O-ring after the compression test (mm) In the above test, t0 = 3.5 mm and t1 = 2.625 mm.

[0215] <ICP plasma weight loss rate> The O-rings (P24 size) prepared in the examples and comparative examples were placed still in the process chamber. The plasma generated using a radical generator was fed into the process chamber, and the O-rings were exposed under the following plasma irradiation conditions. The ICP plasma weight loss rates of O2 and CF4 were calculated from the masses of the O-rings before and after plasma irradiation. (Plasma irradiation conditions) Radical generator: ICP high-density plasma device (RIE-101iPH manufactured by SAMCO) Gas flow rate: 16 sccm Power: 400 W Pressure: 2.66 Pa Irradiation time: 1 hour

[0216] <NF3 Remote Plasma Weight Loss Rate> The O-rings (P24 size) prepared in the examples and comparative examples were placed stationary in the process chamber. Plasma generated using a fluorine radical generator was fed into the process chamber, and the O-rings were exposed under the following plasma irradiation conditions. The NF3 remote plasma weight loss rate was calculated from the mass of the O-rings before and after plasma irradiation. (Plasma Irradiation Conditions) Fluorine radical generator: Astron Atomic Fluorine Generator Model AX7657-2 (manufactured by MKS) Gas flow rate: Ar / NF3 = 1 (L / min) / 1 (L / min) Pressure: 3 Torr Irradiation temperature: 250 °C Irradiation time: 12 hours (the position of the O-ring in the chamber was moved every 2 hours) (Mass Measurement) The mass of the O-rings before and after plasma irradiation was measured using an electronic analytical balance BP211D (manufactured by Sartorius). Then, the NF3 remote plasma weight loss rate was calculated by the following formula. dW = (W0 - W1) / W0 × 100 dW: NF3 remote plasma weight loss rate W0: Mass of the O-ring before plasma irradiation W1: Mass of the O-ring after plasma irradiation

[0217] Example 1 100 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 fluoropolymer 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 on an open roll to prepare a composition. The results are shown in Table 2.

[0218] The obtained composition was pressed at 180°C for 30 minutes to crosslink, and then oven crosslinked in an oven at 290°C for 18 hours to produce an O-ring of P24 size. The obtained O-ring was used to measure the compression set, ICP plasma weight loss rate, and remote plasma weight loss rate by the above-mentioned methods. The results are shown in Table 2.

[0219] Examples 2 to 4 A composition and an O-ring were obtained in the same manner as in Example 1, except that the fluoropolymers shown in Table 2 were used instead of the fluoropolymer obtained in Synthesis Example 1. The results are shown in Table 2.

[0220] Comparative Example 1 A composition and an O-ring were obtained in the same manner as in Example 1, except that the fluoropolymers shown in Table 2 were used instead of the fluoropolymer obtained in Synthesis Example 1. The results are shown in Table 2.

[0221] Comparative Example 2 A composition was obtained in the same manner as in Example 1, except that the fluoropolymer shown in Table 2 was used instead of the fluoropolymer obtained in Synthesis Example 1. The obtained composition showed the MH and ML shown in Table 2. During the preparation of the composition, a phenomenon was observed in which plasticity was gradually lost. The obtained composition was difficult to mold, and it was not possible to prepare an O-ring, measure the compression set and ICP plasma weight loss rate, or measure the remote plasma weight loss rate.

[0222] [Table 2]

[0223] Examples 5 to 6 A composition and an O-ring were obtained in the same manner as in Example 1, except that the fluoropolymers shown in Table 3 were used instead of the fluoropolymer obtained in Synthesis Example 1. The results are shown in Table 3.

[0224] Comparative Example 3 A composition and an O-ring were obtained in the same manner as in Example 1, except that the fluoropolymers shown in Table 3 were used instead of the fluoropolymer obtained in Synthesis Example 1. The results are shown in Table 3.

[0225] [Table 3]

Claims

1. Tetrafluoroethylene units (1) and general formula (2): CF ２ =CF(CF ２ ) ｎ CF=CF ２ (wherein n represents an integer of 2 to 10), The content of the tetrafluoroethylene unit (1) is 98.0 to 99.999 mol % based on the total monomer units constituting the fluoropolymer, The content of the monomer unit (2) is 0.001 to 2.0 mol % based on the total monomer units constituting the fluoropolymer. Fluoropolymer.

2. The fluoropolymer has a peak at 2360-2370 cm obtained by infrared absorption spectroscopy. －１ The peak height (h ０ ) to 1030-1040 cm －１ The peak height (h １ ) spectral intensity ratio (h １ / h ０ 2. The fluoropolymer according to claim 1, wherein the fluoropolymer has a molecular weight of 0.001 or more.

3. The fluoropolymer has a peak at 2360-2370 cm obtained by infrared absorption spectroscopy. －１ The peak height (h ０ ) at 1780-1800 cm －１ The peak height (h ２ ) spectral intensity ratio (h ２ / h ０ 3. The fluoropolymer according to claim 1, wherein the fluoropolymer has a molecular weight of 0.20 or less.

4. The fluoropolymer according to any one of claims 1 to 3, having a peak temperature of 300°C or higher. However, the peak temperature is a temperature corresponding to a maximum value appearing in a differential thermal analysis (DTA) curve obtained by heating the fluoropolymer, which has no history of being heated to a temperature of 300° C. or higher, in air at a temperature of 10° C. / min.

5. The melt viscosity measured at 380°C is 1.0 x 10 ３ ~7.0 x 10 ６ 5. The fluoropolymer according to claim 1, which has a viscosity of 1.0×10 2 to 7.0×10 5 Pa·s.

6. The fluoropolymer according to any one of claims 1 to 5, which is in the form of a powder.

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

8. A composition comprising the fluoropolymer (P) according to any one of claims 1 to 6 and a polymer (E) different from the fluoropolymer (P).

9. The composition according to claim 8, wherein the polymer (E) is a perfluoroelastomer.

10. The composition according to claim 8 or 9, wherein the content of the fluoropolymer (P) is 0.5 to 100 parts by mass based on 100 parts by mass of the polymer (E).

11. The composition according to any one of claims 8 to 10, further comprising at least one selected from the group consisting of inorganic nitrides, organotin compounds, compounds that generate ammonia, and crosslinking agents.

12. A crosslinked product obtained from the composition according to claim 11.

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