WO2022210267A1 - 機能材料および機能材料の製造方法 - Google Patents

機能材料および機能材料の製造方法 Download PDF

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WO2022210267A1
WO2022210267A1 PCT/JP2022/014023 JP2022014023W WO2022210267A1 WO 2022210267 A1 WO2022210267 A1 WO 2022210267A1 JP 2022014023 W JP2022014023 W JP 2022014023W WO 2022210267 A1 WO2022210267 A1 WO 2022210267A1
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fluororubber
functional material
less
particles
material according
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French (fr)
Japanese (ja)
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直樹 渡辺
善宏 瀬戸口
雅則 岡崎
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Valqua Ltd
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Valqua Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4318—Fluorine series
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials

Definitions

  • One embodiment of the present invention relates to a functional material or a method for producing a functional material.
  • polytetrafluoroethylene As an example of the functional material, polytetrafluoroethylene (PTFE) is known for its excellent dielectric properties and low water absorption (eg, Patent Document 1). It is used as a peripheral device part.
  • PTFE polytetrafluoroethylene
  • Patent Document 2 discloses a heat insulating sheet including fibers, silica airgel contained in the fibers, and fibrous cavities.
  • PTFE substrates are used as high-frequency peripheral equipment parts such as antennas in the high-frequency range, but there is still room for improvement in terms of low dielectric constant and low dielectric loss tangent in the high-frequency range of, for example, about 10 GHz.
  • fluororubbers with excellent heat resistance, oil resistance, and chemical resistance, specifically fluoroelastomers (FKM) and perfluoroelastomers (FFKM) has been developed. If fibers having the excellent properties of the fluororubber could be formed, it would be possible to obtain a nonwoven fabric or the like having these properties. The actual situation is that fibers and non-woven fabrics are not known.
  • One embodiment of the present invention is a functional material containing fibers that takes advantage of the properties of fluororubber such as heat resistance, oil resistance, chemical resistance, and flame resistance, while maintaining a low dielectric constant, low dielectric loss tangent, and low thermal conductivity.
  • fluororubber such as heat resistance, oil resistance, chemical resistance, and flame resistance
  • a configuration example of the present invention is as follows.
  • At least one fluororubber selected from fluoroelastomers (FKM) and perfluoroelastomers (FFKM); filler particles containing at least one selected from glass particles, metal oxide particles and mica particles; A functional material containing a fluororubber-based fiber containing.
  • the functional material is a low dielectric material, The functional material according to any one of [1] to [9], wherein the low dielectric material has a dielectric constant ( ⁇ ) of 1.35 or less at a frequency of 10 GHz.
  • the functional material is a low dielectric material, The functional material according to any one of [1] to [10], wherein the low dielectric material has a dielectric loss tangent (tan ⁇ ) of 0.015 or less at a frequency of 10 GHz.
  • a method of manufacturing a functional material comprising:
  • step 2 is a step of irradiating the fibers obtained in the step 1 with radiation.
  • a material containing fibers that takes advantage of the properties of fluororubber such as heat resistance, oil resistance, chemical resistance, and flame retardancy, has a low dielectric constant, a low dielectric loss tangent, and a low heat resistance.
  • Functional materials can be provided that are conductive.
  • FIG. 1 is an SEM image at a magnification of 100 times of the fluororubber-based fiber (nonwoven fabric) obtained in Example 1 after electron beam irradiation.
  • FIG. 2 is an SEM image at a magnification of 1000 of the fluororubber-based fiber (non-woven fabric) obtained in Example 1 after electron beam irradiation.
  • FIG. 3 is an SEM image at a magnification of 3000 times of the fluororubber-based fiber (nonwoven fabric) obtained in Example 1 after electron beam irradiation.
  • FIG. 4 is an SEM image at a magnification of 10,000 times of the fluororubber-based fiber (nonwoven fabric) obtained in Example 1 after electron beam irradiation.
  • FIG. 1 is an SEM image at a magnification of 100 times of the fluororubber-based fiber (nonwoven fabric) obtained in Example 1 after electron beam irradiation.
  • FIG. 2 is an SEM image at a magn
  • FIG. 5 is an SEM image at a magnification of 10,000 times of the fluororubber-based fiber (nonwoven fabric) obtained in Example 2 after electron beam irradiation.
  • FIG. 6 is an SEM image at a magnification of 10,000 times of the fluororubber-based fiber (nonwoven fabric) obtained in Example 3 after electron beam irradiation.
  • a functional material according to one embodiment of the present invention (hereinafter also referred to as “this material”) comprises at least one fluororubber selected from fluoroelastomers (FKM) and perfluoroelastomers (FFKM), glass particles, metal oxide fluororubber-based fibers containing filler particles containing at least one selected from fluorocarbon particles and mica particles.
  • FKM fluoroelastomers
  • FFKM perfluoroelastomers
  • glass particles glass particles
  • the present material is not particularly limited as long as it contains the fluororubber-based fiber, and the fluororubber-based fiber may be the fluororubber-based fiber as it is, or the fluororubber-based fiber is subjected to a plating treatment or the like. Anything is fine. It is preferable that the present material consist of (only) the fluororubber-based fibers, or (only) the fluororubber-based fibers processed by plating or the like.
  • the fluororubber-based fiber contained in the present material may be one, or two or more.
  • a yarn obtained by twisting a plurality of the fibers may be used, but a nonwoven fabric or a woven fabric composed of a plurality of the fluororubber fibers is preferable, and a nonwoven fabric composed of a plurality of the fluororubber fibers. is more preferred.
  • the present material may also be used as a reinforcing material or additive for resin moldings.
  • This material is a material that has the function (characteristics) of fluororubber and the function of filler particles, and is specifically a low dielectric material or a heat insulating material.
  • the dielectric constant ( ⁇ ) of the low dielectric material at a frequency of 10 GHz is preferably 1.35 or less, more preferably 1.30 or less.
  • the lower limit of the dielectric constant is not particularly limited, it is 1, for example.
  • a functional material having a dielectric constant within the above range can be said to have a low dielectric constant and can be suitably used for the following applications.
  • the dielectric loss tangent (tan ⁇ ) of the low dielectric material at a frequency of 10 GHz is preferably 0.015 or less, more preferably 0.010 or less, and still more preferably 0.005 or less.
  • a functional material having a dielectric loss tangent within the above range can be said to have a low dielectric loss tangent and can be suitably used for the following applications.
  • the dielectric constant and dielectric loss tangent can be measured by the methods described in the following examples.
  • the application of the low-dielectric material is not particularly limited, but from the viewpoint of exhibiting the effects of the present invention, it is preferably an electronic circuit board, more preferably a mobile phone, a computer. , wiring boards for modules such as antennas, particularly preferably wiring boards for millimeter-wave antennas (high-frequency wiring boards).
  • this material is used for a wiring board of a millimeter wave antenna, it is possible to effectively utilize the properties of this material such as the dielectric constant.
  • the present material is a low dielectric material
  • the low dielectric material can also be used as a material that requires flexibility, stretchability, etc., such as flexible substrates (eg, flexible printed circuit boards) and wearable members.
  • the heat-insulating material when the present material is a heat-insulating material, the heat-insulating material, particularly when the heat-insulating material is a non-woven fabric, preferably has a thermal conductivity of 0.025 W/m ⁇ K or less, more preferably 0.020 W/m. ⁇ K or less.
  • the present material having a thermal conductivity within the above range can be said to be a heat insulating material and can be suitably used as a heat insulating material.
  • the nonwoven fabric can have a thermal conductivity within the above range even if the thickness is 1 mm or less, or even 0.1 mm or less. Specifically, the thermal conductivity can be measured by the method described in Examples below.
  • the use of the heat insulating material is not particularly limited, but from the viewpoint that the effect of the present invention is more exhibited, it is preferably used as a heat insulating material for various equipment in the automobile industry, the semiconductor industry, etc. mentioned.
  • the present material is a heat insulating material
  • the heat insulating material can also be used as a heat insulating material for various devices that require flexibility, stretchability, and the like.
  • the fluororubber-based fiber comprises at least one fluororubber selected from fluoroelastomers (FKM) and perfluoroelastomers (FFKM), and at least one filler particle selected from glass particles, metal oxide particles and mica particles. including.
  • the fluororubber is at least one selected from fluoroelastomers (FKM) and perfluoroelastomers (FFKM). Among these, FKM is preferable because it is easy to spin.
  • the fluororubber is at least one selected from FKM and FFKM, and at least one selected from FKM and FFKM is at least one selected from crosslinked FKM and crosslinked FFKM.
  • FKM fluoroelastomers
  • FFKM perfluoroelastomers
  • FKM is preferable because it is easy to spin.
  • the fluororubber is at least one selected from FKM and FFKM, and at least one selected from FKM and FFKM is at least one selected from crosslinked FKM and crosslinked FFKM.
  • FFKM is not particularly limited, but includes polymers that do not contain hydrogen atoms (carbon-hydrogen bonds) in the polymer main chain (excluding the terminal), specifically, tetrafluoroethylene (TFE) - perfluorovinyl ether system
  • TFE tetrafluoroethylene
  • FFKM is not particularly limited, but includes polymers that do not contain hydrogen atoms (carbon-hydrogen bonds) in the polymer main chain (excluding the terminal), specifically, tetrafluoroethylene (TFE) - perfluorovinyl ether system
  • TFE tetrafluoroethylene
  • perfluorovinyl ether examples include perfluoro(alkyl vinyl ether) and perfluoro(alkoxyalkyl vinyl ether).
  • perfluoro(alkyl vinyl ether) examples include compounds in which the number of carbon atoms in the alkyl group is, for example, 1 to 10. Specific examples include perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro Fluoro(propyl vinyl ether) is mentioned, preferably perfluoro(methyl vinyl ether).
  • FFKM can be imparted with crosslinkability by including a structural unit derived from a monomer containing a crosslinkable site.
  • the cross-linking site means a site capable of cross-linking reaction, and includes, for example, a nitrile group, a halogen group (eg, I group, Br group), and a perfluorophenyl group.
  • cross-linking site monomers having a nitrile group as a cross-linking site include nitrile group-containing perfluorovinyl ethers.
  • cross-linking site-containing monomer having a halogen group as a cross-linking site examples include halogen group-containing perfluorovinyl ether. A substituted compound and the like can be mentioned.
  • the content of structural units derived from TFE is preferably 50.0 to 79.9 mol%
  • the content of structural units derived from perfluorovinyl ether is preferably 20.0 to 46.9 mol%
  • crosslinked The content of structural units derived from site-containing monomers is preferably 0.1 to 2.0 mol %.
  • FKM fluoroelastomers other than the FFKM, and are not particularly limited, but specific examples include vinylidene fluoride-hexafluoropropylene-based polymer; vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-based polymer; Tetrafluoroethylene-propylene polymer; Vinylidene fluoride-propylene-tetrafluoroethylene polymer; Ethylene-tetrafluoroethylene-perfluoromethyl vinyl ether polymer; Vinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether polymer and vinylidene fluoride-perfluoromethyl vinyl ether polymer.
  • the FKM may contain structural units derived from the crosslinkable site-containing monomer, as in the section for the FFKM.
  • the Mooney viscosity (ML1+10) of the fluorororubber at 121° C. measured according to ASTM D 1646 is preferably 15 or more, more preferably 20 or more, and preferably 150 or less.
  • Mooney viscosity of the fluororubber is in the above range, it is preferable because it is easy to spin, and the fiber shape (porous shape, non-woven fabric shape) formed in the spinning step can be maintained without performing a cross-linking step after the spinning step. .
  • the fluororubber has a Mooney viscosity (ML1+10) of less than 15 at 121°C measured in accordance with ASTM D 1646, it is not easy to form a fiber shape (porous shape, nonwoven shape) by a spinning process. There is a tendency.
  • the Mooney viscosity is the viscosity of the fluororubber before crosslinking.
  • the weight-average molecular weight of the fluororubber measured by gel permeation chromatography is preferably 1 ⁇ 10 because it has excellent solubility and spinning stability and can easily obtain fibers with excellent mechanical strength. 3 or more, more preferably 1 ⁇ 10 4 or more, preferably 5 ⁇ 10 7 or less, more preferably 1 ⁇ 10 7 or less.
  • the fluorine content in the fluororubber is preferably 55% by mass or more, more preferably 62% by mass or more, particularly preferably 64% by mass or more, and preferably 80% by mass or less, more preferably 78% by mass or less. be.
  • the fluorine content can be measured/calculated by solid-state nuclear magnetic resonance (NMR), mass spectrometry (MS spectrum method), or the like.
  • the content of the fluororubber in the fluororubber-based fiber is preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 99% by mass or less, more preferably 90% by mass. % by mass or less, particularly preferably 70% by mass or less.
  • the content of the fluororubber is within the above range, it is possible to easily obtain a fiber that exhibits the physical properties of the fluororubber, such as chemical resistance and heat resistance, and to produce a fiber that utilizes the properties of the fluororubber.
  • a functional material having a low dielectric constant, a low dielectric loss tangent, and a low thermal conductivity can be easily obtained while being a material containing
  • the filler particles contain at least one selected from glass particles, metal oxide particles and mica particles.
  • the filler particles may be solid inorganic particles, hollow inorganic particles, or porous inorganic particles. One type or two or more types of filler particles may be contained in the present material.
  • the metal oxide particles include silica particles and zirconia particles.
  • the filler particles preferably contain at least one selected from glass particles and metal oxide particles from the viewpoint that a low dielectric material having a lower dielectric constant and a lower dielectric loss tangent can be easily obtained. , silica particles and glass particles are more preferable.
  • the filler particles preferably contain at least one selected from silica particles, glass particles and mica particles from the viewpoint that a heat insulating material having a lower thermal conductivity can be easily obtained. At least one selected from particles and glass particles is more preferred, and silica particles are particularly preferred.
  • silica particles as the filler particles, when forming fibers (nonwoven fabric) on a collector made of aluminum or the like in step 1 below, the fibers (nonwoven fabric) formed on the collector and the collector The fibers (non-woven fabric) can be easily peeled off from the collector. Further, by using silica particles as the filler particles, it is possible to easily obtain fluororubber fibers having excellent linearity, and to suppress adhesion between the obtained fluororubber fibers. One type or two or more types of filler particles may be contained in the present material.
  • the average particle diameter of the filler particles measured by the BET method in accordance with JIS Z 8830: 2013 is such that a functional material having a lower dielectric constant, a lower dielectric loss tangent and a lower thermal conductivity can be easily obtained. From the point of view, it is preferably 1 nm or more and preferably 100 nm or less.
  • the average particle size of the filler particles measured by the BET method in accordance with JIS Z 8830:2013 is more It is preferably 10 nm or more, particularly preferably 30 nm or more, more preferably 70 nm or less, and particularly preferably 60 nm or less.
  • the average particle size of the filler particles measured by the BET method in accordance with JIS Z 8830:2013 is more preferably 5 nm or more, because a material with a lower thermal conductivity can be easily obtained. It is more preferably 10 nm or more, more preferably 50 nm or less, still more preferably 40 nm or less, and particularly preferably 30 nm or less.
  • the filler particles may be particles that have undergone a surface treatment such as a hydrophobic treatment.
  • the particles themselves may be used, or a dispersion liquid obtained by dispersing the particles in a dispersion medium may be used. Examples of the latter case include, when the filler particles are silica particles, silica sols such as organosilica sols in which silica particles are dispersed in an organic solvent.
  • the content of the filler particles in the fluororubber-based fiber is preferably 1% by mass or more, more preferably 10% by mass or more, particularly preferably 30% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably 60% by mass or less.
  • a functional material with low dielectric constant, low dielectric loss tangent and low thermal conductivity can be easily obtained.
  • the fluororubber-based fiber may optionally contain other conventionally known additives blended into the fiber within a range that does not impair the effects of the present invention.
  • other additives include polymers other than the fluororubber (e.g., fluororesin), cross-linking agents, co-cross-linking agents, anti-aging agents, antioxidants, vulcanization accelerators, stabilizers, and silane coupling. agents, fillers other than the filler particles, plasticizers, flame retardants, waxes, and lubricants.
  • Each of the other additives may be used alone or in combination of two or more.
  • the content of the fluororubber with respect to the total 100% by mass of the fluororubber and the polymer in the fluororubber fiber is 50%. % by mass or more.
  • the cross-linking agent may be appropriately selected depending on the fluororubber to be used. , a peroxide-based cross-linking agent, a bisphenol-based cross-linking agent, a triazine-based cross-linking agent, an oxazole-based cross-linking agent, an imidazole-based cross-linking agent, a thiazole-based cross-linking agent, and the like.
  • Peroxide cross-linking agents include, for example, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, di-t-butylperoxide, oxide, t-butyldicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(benzoylperoxy ) hexane, ⁇ , ⁇ '-bis(t-butylperoxy-m-isopropyl)benzene, t-butylperoxyisopropyl carbonate, p-chlorobenzoyl peroxide.
  • co-crosslinking agent a conventionally known co-crosslinking agent (crosslinking aid) can be used.
  • co-crosslinking agent examples include triallyl isocyanurate, triallyl cyanurate, triallyl formal, triallyl trimellitate, N,N'-m-phenylenebismaleimide, dipropargyl terephthalate, diallyl phthalate, and tetraallyl.
  • examples include compounds (polyfunctional monomers) capable of co-crosslinking by radicals such as terephthalamide, and among these, triallyl isocyanurate is preferable from the viewpoint of reactivity and heat resistance of the obtained fiber.
  • the other fillers include, when the present material is a low dielectric material, functional fillers (e.g., thermally conductive particles, reinforcing fibers) according to the application of the low dielectric material, and the present material is a heat insulating material, functional fillers (eg, insulating particles, reinforcing fibers) suitable for the use of the heat insulating material can be used.
  • functional fillers e.g., insulating particles, reinforcing fibers
  • the other fillers include clay, talc, diatomaceous earth, silicic acid compounds (silicates, etc.), calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, and fine resin particles.
  • the shape of the other filler is not particularly limited, and examples thereof include particulate, fibrous, and porous.
  • the content of the other filler is such that the physical properties of the fluororubber such as chemical resistance and heat resistance are exhibited, and the content of the other filler is From the viewpoint of being able to easily obtain a fiber that exhibits its physical properties sufficiently, it is preferably 1 part by mass or more with respect to a total of 100 parts by mass of the fluororubber and filler particles (not other fillers). , more preferably 10 parts by mass or more, particularly preferably 30 parts by mass or more, preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and particularly preferably 60 parts by mass or less.
  • the average fiber diameter of the fluororubber-based fiber is preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less, still more preferably 10 ⁇ m or less, more preferably 0.05 ⁇ m or more, still more preferably 0.1 ⁇ m or more, and particularly preferably is 0.3 ⁇ m or more.
  • the average fiber diameter is within the above range, it is possible to form a nonwoven fabric or the like exhibiting high flexibility, and even when a thin nonwoven fabric or the like is formed, the uniformity of fiber distribution can be increased, which is preferable.
  • the average fiber diameter of the fluororubber-based fiber can be adjusted by appropriately selecting the conditions for forming the fiber. By reducing the nozzle diameter, increasing the applied voltage, or increasing the voltage density, there is a tendency that the average fiber diameter of the obtained fibers can be reduced.
  • the average fiber diameter in this specification is obtained by observing the fiber (group) to be measured with a scanning electron microscope (SEM) (magnification: 2000 times), randomly selecting 20 fibers from the obtained SEM image, It is an average value calculated based on the measurement results obtained by measuring the fiber diameter (major diameter) of each of these fibers.
  • SEM scanning electron microscope
  • the fiber diameter variation coefficient of the fluororubber-based fiber calculated by the following formula is preferably 0.7 or less, more preferably 0.5 or less, and more preferably 0.01 or more.
  • Fiber diameter variation coefficient standard deviation / average fiber diameter ("standard deviation" is the standard deviation of the fiber diameters of the 20 fibers.)
  • the fiber length of the fluororubber-based fiber is not particularly limited, but is preferably 0.1 mm or longer, more preferably 0.5 mm or longer, still more preferably 1 mm or longer, preferably 1000 mm or shorter, more preferably 100 mm or shorter, and still more preferably. is 50 mm or less.
  • This material is preferably a nonwoven fabric containing the fluororubber-based fiber.
  • the nonwoven fabric is not particularly limited as long as it contains the fluororubber-based fibers, but examples thereof include nonwoven fabrics made of (only) the fibers.
  • the porosity of the nonwoven fabric is not particularly limited, it is, for example, 0.1% by volume or more, preferably 30% by volume or more, and is, for example, 95% by volume or less, preferably 90% by volume or less.
  • the basis weight of the nonwoven fabric is preferably 100 g/m 2 or less, more preferably 80 g/m 2 or less, and more preferably 1 g/m 2 or more.
  • the thickness of the nonwoven fabric may be appropriately selected according to the use of the nonwoven fabric, and is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and preferably 1 mm or less, more preferably 500 ⁇ m or less.
  • the nonwoven fabric is formed by accumulating the fibers in the form of a sheet.
  • Such a nonwoven fabric may be composed of a single layer, or may be composed of two or more layers having different materials and fiber diameters.
  • the method for producing this material is not particularly limited as long as a fibrous material containing the fluororubber and filler particles can be formed, but production including step 1 of spinning a fluororubber composition containing the fluororubber and filler particles A method is preferred. Such a method is preferable because it is difficult for filler particles to fall off from the present material to be obtained.
  • Step 1 Examples of the step 1 include an electrospinning method, a melt spinning method, a melt electrospinning method, and a spunbond method (melt blowing method).
  • an electrospinning method and a melt spinning method are preferable.
  • a fiber having a desired shape can be easily spun, a fiber having a small fiber diameter can be obtained, and a nonwoven fabric or the like obtained using the fiber tends to have a high porosity and a high specific surface area.
  • the electrospinning method is particularly preferred.
  • the obtained fibers may be formed on a (fiber collection) collector, and in this case, a non-woven fabric is formed on the collector. Therefore, one aspect of the method for producing this material is also a method for producing a nonwoven fabric.
  • a fluororubber-based composition containing the fluororubber, the filler particles, and, if necessary, a solvent is preferably used.
  • the proportion of the fluororubber contained in the fluororubber-based composition is preferably 5% by mass or more, more preferably 10% by mass or more, for example 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less. % by mass or less.
  • the fluororubber may be used singly or in combination of two or more.
  • the proportion of the filler particles contained in the fluororubber-based composition is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, for example 80% by mass or less, preferably 70% by mass. % or less, more preferably 60 mass % or less.
  • the filler particles may be used singly or in combination of two or more.
  • the solvent is not particularly limited as long as it can dissolve or disperse the fluororubber. Benzene, sulfolane, methanol, ethanol, phenol, pyridine, propylene carbonate, acetonitrile, trichloroethane, hexafluoroisopropanol, diethyl ether. One of these solvents may be used alone, or a mixed solvent in which two or more of them are combined may be used.
  • the amount of the solvent used is, for example, 0% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, preferably 90% by mass or less, and more preferably 100% by mass of the fluororubber-based composition. is 80% by mass or less.
  • the fluororubber-based composition may further contain other additives such as surfactants, dispersants, charge control agents, viscosity control agents, and fiber-forming agents. Each of these other components may be used alone or in combination of two or more.
  • a fluororubber-based composition containing a cross-linking agent and/or a co-cross-linking agent may be used, and a fluoro-rubber-based composition that does not contain a cross-linking agent and/or a co-cross-linking agent Compositions may be used.
  • a cross-linking agent and/or a co-cross-linking agent if Step 2 below is not performed, the cross-linking agent or co-cross-linking agent may become impurities and the tensile properties of the fiber may deteriorate, so Step 2 below is performed. is preferred.
  • cross-linking agent and co-cross-linking agent examples include the same cross-linking agents and co-cross-linking agents as those described in the column of the other additives.
  • the amount of the cross-linking agent used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 30 parts by mass or less, more preferably 100 parts by mass of the fluororubber. It is 10 parts by mass or less.
  • the amount of the co-crosslinking agent used relative to 100 parts by mass of the fluororubber is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 30 parts by mass or less. Preferably, it is 10 parts by mass or less.
  • the fiber-forming agent is preferably an organic polymer having high solubility in a solvent.
  • Acrylamide, cellulose, polyvinyl alcohol is a polymer having high solubility in a solvent.
  • the amount used depends on the viscosity of the solvent and the solubility in the solvent. % or more, for example, 15% by mass or less, preferably 10% by mass or less.
  • Conditions for electrospinning include, for example, the following conditions.
  • the applied voltage (voltage applied between the spinning nozzle and the collector) is preferably 1 kV or higher, more preferably 5 kV or higher, still more preferably 10 kV or higher, and preferably 100 kV or lower, more preferably 50 kV or lower, further preferably 40 kV or lower.
  • the spinning distance (distance between spinning nozzle and collector) is preferably between 5 and 30 cm.
  • the discharge rate of the fluororubber-based composition is preferably 0.01 to 3 ml/min.
  • the tip diameter (outer diameter) of the spinning nozzle used for electrospinning is preferably 0.1 mm or more, more preferably 0.2 mm or more, and preferably 2.0 mm or less, more preferably 1.6 mm or less.
  • the spinning atmosphere does not have to be particularly controlled, but it is preferable that the relative humidity is, for example, 10 to 50% and the temperature is, for example, 10 to 35°C.
  • a rotating collector or a flat plate can be used as the collector.
  • the fibers ejected from the spinning nozzle are wound around the drum by rotating the drum, and a nonwoven fabric in which the fibers are oriented in a certain direction can be obtained.
  • the rotation speed of the rotating collector is, for example, 50 to 5,000 revolutions/minute.
  • a nonwoven fabric made of non-oriented fibers can be obtained by using a flat collector.
  • melt spinning can be performed, for example, by melting the fluororubber-based composition with heat, extruding it from a spinneret (nozzle) to make it fibrous, and then cooling it.
  • a specific method of melt spinning is not particularly limited, and a known method can be used depending on the raw material to be used.
  • the fluororubber-based composition used for melt spinning is not particularly limited as long as it includes the fluororubber and filler particles, and may be the same composition as the composition described in the electrospinning section.
  • a step of forming fibers by an electrospinning method or the like and a step of accumulating the formed fibers into a sheet to form a nonwoven fabric. It may be performed at the same time, or after performing the step of forming fibers, using the formed fibers, a wet papermaking method, a water punch method, a chemical bond method, a thermal bond method, a spun bond method, a needle punch method, a stitch bond
  • a process of forming a nonwoven fabric by accumulating in a sheet shape may be performed by a method or the like.
  • Step 2 When producing this material, only the step 1 may be performed, but the fiber shape (porous shape, non-woven fabric shape) obtained in step 1 can be maintained for a long time, and the tensile strength and tensile elastic modulus It is preferable to include the step 2 of cross-linking the fibers obtained in the step 1 from the viewpoint that fibers with improved tensile properties such as can be easily obtained. Through such step 2, a fiber containing at least one selected from crosslinked FKM and crosslinked FFKM can be obtained.
  • Step 2 include a step of irradiating the fibers obtained in Step 1 with radiation (radiation cross-linking) and a step of heating the fibers obtained in Step 1 (thermal cross-linking).
  • radiation cross-linking is preferable because cross-linking treatment can be performed in a short time and the fiber shape (porous shape, non-woven fabric shape) obtained in step 1 can be easily maintained.
  • the fibers obtained in step 1 may be fibers immediately after being extruded from the nozzle or the like, or may be fibers after being accumulated on a collector or the like.
  • Radiation Crosslinking examples include X-rays, gamma rays, electron beams, proton beams, neutron beams, heavy particle beams, alpha rays, and beta rays. Among these, electron beams are preferred.
  • One type of radiation may be used alone, or two or more types may be used.
  • the method of radiation crosslinking may be performed by a conventionally known method, and the conditions for electron beam irradiation include, for example, the following conditions. It is desirable to irradiate the electron beam so that the absorbed dose is preferably 10 kGy or more, more preferably 20 kGy or more, preferably 500 kGy or less, more preferably 300 kGy or less. When irradiating with radiation, it is preferable to carry out the irradiation in an atmosphere of an inert gas such as nitrogen or argon because the cross-linking reaction is less likely to be inhibited and a fiber having excellent mechanical properties can be easily obtained. .
  • an inert gas such as nitrogen or argon
  • the heating conditions in the thermal crosslinking may be set according to the composition of the fluororubber-based composition used, for example, the heating temperature is 150 to 200 ° C. and the heating time is 1 to 24 hours. be done.
  • Example 1 Methyl ethyl ketone (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) is added to FKM (Daiel G901H, manufactured by Daikin Industries, Ltd.) so that the concentration is 20% by mass. Mooney viscosity at 121 ° C. measured according to ASTM D 1646 A fluororubber composition was prepared by dissolving (ML1+10):135). The prepared fluororubber-based composition and MEK-ST-40 (manufactured by Nissan Chemical Industries, Ltd., silica content: 40% by mass, average particle size of silica: 12 nm) were mixed so that the mass ratio of FKM to silica was 1. : 1 to prepare a mixed solution. The average particle size of silica was measured by the BET method in accordance with JIS Z 8830:2013.
  • an electrospinning device manufactured by MEC Co., Ltd. was used to directly spin fluororubber fibers onto a collector attached with aluminum foil under the following conditions.
  • the obtained fluororubber-based fiber was observed by SEM (S-3400N, manufactured by Hitachi High-Technologies Corporation, the same device was used for the following SEM), and after confirming that it had a fiber shape,
  • the fluororubber-based fibers were irradiated with an electron beam (EB) using an EB apparatus (CB250/30/20mA, manufactured by Iwasaki Electric Co., Ltd.).
  • EB electron beam
  • the electron beam was irradiated at room temperature (21° C.) under N 2 so that the absorbed dose was 100 kGy.
  • the conveying speed was 5 m/min.
  • the average fiber diameter of the obtained fluororubber fibers was about 2 ⁇ m.
  • the fluororubber-based fibers after electron beam irradiation were observed with an SEM at magnifications of 100, 1,000, 3,000, and 10,000. SEM images of each are shown in FIGS.
  • the SEM images in FIGS. 1 to 4 can be said to be images of the obtained fibers as well as images of the obtained nonwoven fabric.
  • the thickness of the obtained nonwoven fabric was about 100 ⁇ m.
  • Example 2 In Example 1, instead of MEK-ST-40, MEK-ST-L (manufactured by Nissan Chemical Industries, Ltd., silica content: 30% by mass, average particle size of silica: 45 nm) was used, and FKM and silica were combined. A mixed solution was prepared by mixing so that the mass ratio of was 1:1. A fluororubber fiber was obtained and irradiated with an electron beam in the same manner as in Example 1 except that the prepared mixed solution was used. The fluororubber-based fiber after electron beam irradiation was observed using an SEM at a magnification of 10,000. A SEM image at this time is shown in FIG. The average fiber diameter of the obtained fluororubber-based fibers was about 1.5 ⁇ m, and the thickness of the obtained nonwoven fabric was about 100 ⁇ m.
  • Example 3 In Example 1, MEK-ST-ZL (manufactured by Nissan Chemical Industries, Ltd., silica content: 30% by mass, average particle size of silica: 80 nm) was used instead of MEK-ST-40, and FKM and silica were combined. A mixed solution was prepared by mixing so that the mass ratio of was 1:1. A fluororubber fiber was obtained and irradiated with an electron beam in the same manner as in Example 1 except that the prepared mixed solution was used. The fluororubber-based fiber after electron beam irradiation was observed using an SEM at a magnification of 10,000. A SEM image at this time is shown in FIG. The average fiber diameter of the obtained fluororubber-based fibers was about 1.5 ⁇ m, and the thickness of the obtained nonwoven fabric was about 100 ⁇ m.
  • Example 4 A fluororubber-based fiber was obtained and irradiated with an electron beam in the same manner as in Example 1, except that the discharge time was changed to 30 minutes.
  • the thickness of the obtained nonwoven fabric was 60 ⁇ m.
  • Comparative Example 2 As Comparative Example 2, a PTFE film (VALFLON cutting tape 7900, manufactured by Valqua Co., Ltd., thickness 100 ⁇ m) was used.
  • Example 3 A fluororubber fiber was obtained and irradiated with an electron beam in the same manner as in Example 1, except that MEK-ST-40 was not used.
  • the average fiber diameter of the obtained fluororubber-based fibers was about 1.5 ⁇ m, and the thickness of the obtained nonwoven fabric was 100 ⁇ m.
  • Relative permittivity and dielectric loss tangent Relative permittivity and dielectric constant of the fluorororubber fiber (nonwoven fabric) after electron beam irradiation obtained in Examples 1 to 3, the fluororubber film obtained in Comparative Example 1, and the PTFE film used as Comparative Example 2 Tangent was measured as follows. Table 1 shows the results.
  • PNA-X network analyzer N5245B manufactured by Keysight Technologies
  • split cylinder resonator 85072A manufactured by Keysight Technologies
  • material measurement software N1500A manufactured by Keysight Technologies
  • IPC-TM-650 2.5.5 .13 the dielectric constant and dielectric loss tangent were measured under the conditions of a frequency of 10 GHz, a temperature of 23° C. ⁇ 2° C., and a humidity of 50 ⁇ 10% RH.
  • the thermal conductivity of the fluororubber fibers (nonwoven fabric) after electron beam irradiation obtained in Examples 1 and 4 and Comparative Example 3 was measured using Thermolab (KES-F7, manufactured by Kato Tech Co., Ltd.) as follows. measured as Table 2 shows the results. First, the device was turned on and allowed to warm up for 30 minutes. After that, the base temperature of the thermocool (constant temperature table) located under the BT-Box (5 ⁇ 5) was adjusted to 20.0°C. After the BT-Box and the guard plate for preventing heat leakage from the four sides of the BT-Box reached 30 ° C., the sample (electrons obtained in Examples 1, 4 and Comparative Example 3) was placed on the thermocool.
  • Non-woven fabric after irradiation was placed, and the BT-Box was placed thereon so that the hot plate of the BT-Box was in contact with the sample. After that, the temperature of the BT-Box was adjusted to 30° C., the temperature of the guard plate was adjusted to 30° C., and the average heat flow through the BT-Box was measured for 60 seconds.
  • the thermal conductivity k (W/m ⁇ K) of the sample was calculated from the following formula.
  • the fibers obtained in Examples maintained their fiber shapes even after electron beam irradiation, and that silica was present in the fibers.
  • the fibers (nonwoven fabrics) obtained in the examples had no powder falling of silica from the fibers (nonwoven fabrics), and had both flexibility and followability to the contact object.
  • the nonwoven fabrics obtained in the examples exhibit a low dielectric constant and a low dielectric loss tangent.
  • the nonwoven fabrics obtained in Examples are considered to exhibit excellent heat insulating performance due to their porosity and fine voids between silica in the fibers. In particular, when silica having an average particle size of 1 to 50 nm was used, the heat insulating performance was improved even when the film was made thinner (low thermal conductivity).

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JPH07500386A (ja) * 1991-10-17 1995-01-12 ダブリュ．エル．ゴア　アンド　アソシエーツ，インコーポレイティド 連続ポリテトラフルオロエチレンファイバー
WO2009018463A2 (en) * 2007-08-01 2009-02-05 Donaldson Company, Inc. Fluoropolymer fine fiber
JP2013520584A (ja) * 2010-10-14 2013-06-06 ゼウス インダストリアル プロダクツ インコーポレイテッド 抗菌基質
WO2021246218A1 (ja) * 2020-06-05 2021-12-09 株式会社バルカー フッ素ゴム繊維、フッ素ゴム不織布およびフッ素ゴム繊維の製造方法

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JPS5959909A (ja) * 1982-09-29 1984-04-05 Daikin Ind Ltd ゴム弾性フイラメント
JPH07500386A (ja) * 1991-10-17 1995-01-12 ダブリュ．エル．ゴア　アンド　アソシエーツ，インコーポレイティド 連続ポリテトラフルオロエチレンファイバー
WO2009018463A2 (en) * 2007-08-01 2009-02-05 Donaldson Company, Inc. Fluoropolymer fine fiber
JP2013520584A (ja) * 2010-10-14 2013-06-06 ゼウス インダストリアル プロダクツ インコーポレイテッド 抗菌基質
WO2021246218A1 (ja) * 2020-06-05 2021-12-09 株式会社バルカー フッ素ゴム繊維、フッ素ゴム不織布およびフッ素ゴム繊維の製造方法

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