WO2021246218A1 - 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 - Google Patents

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 Download PDF

Info

Publication number
WO2021246218A1
WO2021246218A1 PCT/JP2021/019563 JP2021019563W WO2021246218A1 WO 2021246218 A1 WO2021246218 A1 WO 2021246218A1 JP 2021019563 W JP2021019563 W JP 2021019563W WO 2021246218 A1 WO2021246218 A1 WO 2021246218A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
fluororubber
fkm
fibers
cross
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/019563
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
直樹 渡辺
善宏 瀬戸口
雅則 岡崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Valqua Ltd
Original Assignee
Valqua Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Valqua Ltd filed Critical Valqua Ltd
Priority to JP2022528754A priority Critical patent/JP7772696B2/ja
Publication of WO2021246218A1 publication Critical patent/WO2021246218A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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

Definitions

  • One embodiment of the present invention relates to a fluororubber fiber, a fluororubber non-woven fabric, or a method for producing a fluororubber fiber.
  • fibers are formed from the fluororesin, and the fibers are used as a non-woven fabric or the like as a filter or a printed circuit board (eg, Patent Documents 1 and 2).
  • fluororubber with excellent heat resistance, oil resistance, chemical resistance, etc., in response to strict requirements in fields such as the automobile industry, aerospace industry, oil / gas drilling industry, semiconductor industry, and medical industry.
  • Fluoroelastomer (FKM) and perfluoroelastomer (FFKM) have been developed in the industry.
  • fibers having excellent properties of the fluororubber can be formed, it is considered that a non-woven fabric or the like having these properties can be obtained.
  • fluororubber is currently available. The reality is that the fibers and non-woven fabrics made of these products are not known.
  • One embodiment of the present invention provides a fiber and a non-woven fabric that utilize the characteristics of fluororubber such as heat resistance, oil resistance, and chemical resistance.
  • the configuration example of the present invention is as follows.
  • Fluororubber fiber The fluororubber is at least one selected from fluoroelastomer (FKM) and perfluoroelastomer (FFKM). Fluororubber fiber.
  • FKM fluoroelastomer
  • FFKM perfluoroelastomer
  • Step 1 of spinning a fluororubber composition containing at least one fluororubber selected from fluoroelastomer (FKM) and perfluoroelastomer (FFKM), and Step 2 for cross-linking the fibers obtained in step 1 A method for producing a fluororubber fiber, including.
  • a fiber having a fiber shape and a non-woven fabric while taking advantage of the characteristics of fluororubber such as heat resistance, oil resistance, and chemical resistance. Further, according to one embodiment of the present invention, it is possible to provide a flexible and stretchable fiber and a non-woven fabric which can maintain a desired shape such as a fiber shape or a porous shape for a long period of time.
  • FIG. 1 is an SEM image of the fibers (nonwoven fabric) obtained in Examples 1, 3 and Comparative Example 1.
  • FIG. 2 is an SEM image of the fibers (nonwoven fabric) obtained in Examples 4 and 5.
  • the fluororubber fiber (hereinafter, also referred to as “the present fiber”) according to the embodiment of the present invention is at least one fluororubber fiber selected from fluoroelastomere (FKM) and perfluoroelastomere (FFKM).
  • the present fiber may be a fiber made of only the fluororubber, or may be a fiber containing the fluororubber and an additive other than the fluororubber. Further, the present fiber may be a fiber obtained by subjecting these fibers to a plating treatment or a hydrophilic treatment.
  • the content of the fluororubber in the fiber is 50% by mass or more based on 100% by mass of the total of the fluororubber and the polymer. be.
  • one fiber may be used as it is, a plurality of the fibers may be used as a twisted yarn, or may be used as an additive such as a reinforcing material for a resin molded body. It is preferably used as a non-woven fabric or woven fabric using a plurality of fibers, and more preferably used as a non-woven fabric.
  • the fiber can be used as a filter, a separator, a substrate, a base material, etc. for automobile members, aerospace members, chemical plants, semiconductor-related devices, medical members, etc., and according to one embodiment of the present invention, the fiber can be used. Since it is possible to maintain the desired shape such as fiber shape and porous shape for a long period of time and provide flexible and stretchable fibers and non-woven fabrics, the flexibility of flexible substrates (eg, flexible printed circuit boards) and wearable members can be achieved. It can be suitably used as a material that requires elasticity and the like.
  • a fiber or a non-woven fabric which is excellent in breathability and water repellency and is hard to get dirty, and from this point as well, it can be suitably used as a wearable member.
  • the fluororubber is at least one selected from fluoroelastomer (FKM) and perfluoroelastomer (FFKM).
  • FKM fluoroelastomer
  • FFKM perfluoroelastomer
  • FKM is preferable because it is easy to spin.
  • FKM has excellent chemical resistance and heat resistance, and also has excellent resistance to stains, stains, oxidation and ultraviolet rays
  • the fiber can be made into a wearable member.
  • the fluororubber is at least one selected from FKM and FFKM, but at least one selected from FKM and FFKM here is at least one selected from a crosslinked product of FKM and a crosslinked product of FFKM. May include.
  • the fluororubber contained in the fiber is a cross-linked product of FKM. And / or a crosslinked product of FFKM, preferably a crosslinked product of FKM and / or a crosslinked product of FFKM. Two or more types of fluororubber may be contained in this fiber.
  • the FFKM is not particularly limited, and examples thereof include polymers that do not contain a hydrogen atom (carbon-hydrogen bond) in the polymer main chain (excluding the terminal), and specific examples thereof are tetrafluoroethylene (TFE) -perfluorovinyl ether type. Examples thereof include a copolymer, and a copolymer containing a TFE-derived structural unit and a perfluorovinyl ether-derived structural unit, and if necessary, a cross-linking site-containing monomer-derived structural unit is preferable.
  • TFE tetrafluoroethylene
  • perfluorovinyl ether examples include perfluoro (alkyl vinyl ether) and perfluoro (alkoxy alkyl vinyl ether).
  • perfluoro (alkyl vinyl ether) examples include compounds in which the alkyl group has 1 to 10 carbon atoms, and specific examples thereof include perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), and per. Fluoro (propyl vinyl ether) and the like are mentioned, and perfluoro (methyl vinyl ether) is preferable.
  • CF 2 CFOCF 2 CF (CF 3 ) OC n F 2n + 1
  • CF 2 CFO (CF 2 ) 3 OC n F 2n + 1
  • CF 2 CFO CF 2 CF (CF 3 ) O (CF 2 O) m C n F 2n + 1
  • CF 2 CFO (CF 2 ) 2 OC n F 2n + 1
  • n is, for example, 1 to 5
  • m is, for example, 1 to 3, respectively.
  • FFKM can impart crosslinkability to FFKM by containing a structural unit derived from a monomer containing a cross-linking site.
  • the cross-linking site means a site capable of a cross-linking reaction, and examples thereof include a nitrile group, a halogen group (eg, I group, Br group), and a perfluorophenyl group.
  • cross-linking site monomer having a nitrile group as the cross-linking site examples include nitrile group-containing perfluorovinyl ether, and specific examples thereof.
  • cross-linking site-containing monomer having a halogen group as the cross-linking site examples include a halogen group-containing perfluorovinyl ether.
  • the nitrile group is used as the halogen group. Examples include the replaced compound.
  • the content of the constituent unit derived from TFE in FFKM is preferably 50.0 to 79.9 mol%, and the content of the constituent unit derived from perfluorovinyl ether is preferably 20.0 to 46.9 mol%, cross-linking.
  • the content of the structural unit derived from the site-containing monomer is preferably 0.1 to 2.0 mol%.
  • FKM fluoropolymers other than the FFKM
  • examples thereof are vinylidene fluoride-hexafluoropropylene-based polymer; vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-based polymer; Tetrafluoroethylene-propylene polymer; vinylidene fluoride-propylene-tetrafluoroethylene polymer; ethylene-tetrafluoroethylene-perfluoromethylvinyl ether polymer; vinylidene fluoride-tetrafluoroethylene-perfluoromethylvinyl ether-based weight
  • examples thereof include a combined, vinylidene fluoride-perfluoromethylvinyl ether-based polymer.
  • FKM may contain a structural unit derived from a monomer containing a cross-linking site, similar to the column of 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 100 or less.
  • the Mooney viscosity of the fluororubber is within the above range, 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, which is preferable. ..
  • the Mooney viscosity is the viscosity of the fluororubber before cross-linking when the fluororubber is a crosslinked body.
  • the weight average molecular weight of the fluororubber measured by the gel permeation chromatograph method is preferably 1 ⁇ 10 from the viewpoints that fibers having excellent solubility and spinning stability and excellent mechanical strength can be easily obtained. It is 3 to 5 ⁇ 10 7 , more preferably 1 ⁇ 10 4 to 1 ⁇ 10 7 .
  • 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, preferably 80% by mass or less, and more preferably 78% by mass or less. be.
  • the fluorine content can be measured and calculated by a solid-state nuclear magnetic resonance method (NMR), a mass spectrometry method (MS spectral method), or the like.
  • the content of fluororubber in the fiber is preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 50% by mass or more, and the upper limit of the content is not particularly limited, but the fiber can be used. When the following filler is not included, it may be 100% by mass. When the content of the fluororubber is within the above range, it is possible to easily obtain a fiber in which the physical properties such as chemical resistance and heat resistance of the fluororubber are more exhibited.
  • the fiber may contain other conventionally known additives that have been blended into the fiber, if necessary, as long as the effects of the present invention are not impaired.
  • the other additives include polymers other than the fluororubber (eg, fluororesin), cross-linking agents, co-cross-linking agents, antioxidants, antioxidants, vulcanization accelerators, stabilizers, and silane couplings.
  • examples include agents, fillers (reinforcing agents), plasticizers, flame retardants, waxes, and lubricants.
  • the other additives only one kind may be used, or two or more kinds may be used.
  • the cross-linking agent may be appropriately selected depending on the fluororubber used. For example, when FKM is used, a peroxide-based cross-linking agent, a polyamine-based cross-linking agent, a polyol-based cross-linking agent and the like can be mentioned, and when FFKM is used. , Peroxide-based cross-linking agent, bisphenol-based cross-linking agent, triazine-based cross-linking agent, oxazole-based cross-linking agent, imidazole-based cross-linking agent, thiazole-based cross-linking agent and the like.
  • peroxide-based cross-linking agent examples include 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, and di-t-butylper.
  • Oxide t-butyldicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5- (t-butylperoxy) hexin-3, 2,5-dimethyl-2,5-di (benzoyl peroxide) ) 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-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, and tetraallyl terephthalate.
  • examples thereof include compounds (polyfunctional monomer) capable of co-crosslinking with radicals such as amides, and among these, it is preferable to contain triallyl isocyanurate from the viewpoint of reactivity and heat resistance of the obtained fiber.
  • the filler examples include functional fillers (eg, thermally conductive particles, conductive particles, insulating particles, reinforcing fibers) according to the use of the present fiber, and specifically, a carbon material (eg, a carbon material (reinforcing fiber).
  • a carbon material eg, a carbon material (reinforcing fiber).
  • Examples thereof include calcium, mica, aluminum hydroxide, metal (eg, silver) particles, and resin fine particles.
  • the shape of the filler is not particularly limited, and examples thereof include particles and fibers.
  • the content of the filler in the fiber exhibits the physical properties such as chemical resistance and heat resistance of the fluororubber, and the physical properties of the filler are fully exhibited. It is preferably 0.1 to 80% by mass, and more preferably 1 to 70% by mass from the viewpoint that the fiber to be obtained can be easily obtained.
  • the average fiber diameter of the present fiber is preferably 50 ⁇ m or less, more preferably 0.05 to 50 ⁇ m, still more preferably 0.1 to 20 ⁇ m, and particularly preferably 0.3 to 10 ⁇ m.
  • the average fiber diameter is within the above range, a non-woven fabric or the like showing high flexibility can be formed, and even when a thin non-woven fabric or the like is formed, the distribution uniformity of the fibers can be improved, which is preferable.
  • the average fiber diameter of this fiber can be adjusted by appropriately selecting the conditions for forming the fiber. For example, in the case of manufacturing by the electrospinning method, the nozzle diameter that lowers the humidity during electrospinning is adjusted. There is a tendency that the average fiber diameter of the obtained fiber can be reduced by reducing the value, increasing the applied voltage, or increasing the voltage density.
  • the average fiber diameter in the present specification 20 fibers are randomly selected from the obtained SEM images obtained by observing the fibers (group) to be measured with a scanning electron microscope (SEM) (magnification: 2000 times). The fiber diameter (major axis) of each of these fibers is measured, and it is an average value calculated based on the measurement result.
  • SEM scanning electron microscope
  • the coefficient of variation of the fiber diameter of this fiber calculated by the following formula is preferably 0.7 or less, more preferably 0.01 to 0.5.
  • the coefficient of variation of the fiber diameter is within the above range, the fiber diameter becomes uniform, the mechanical strength is excellent, and the non-woven fabric or the like obtained by using the fiber has a higher porosity.
  • Coefficient of variation of fiber diameter standard deviation / average fiber diameter (Note that the "standard deviation” is the standard deviation of the fiber diameters of the 20 fibers).
  • the fiber length of this fiber is not particularly limited, but is preferably 0.1 to 1000 mm, more preferably 0.5 to 100 mm, and even more preferably 1 to 50 mm.
  • the method for producing the present fiber is not particularly limited as long as it can form a fibrous substance containing FKM and / or FFKM, but the step 1 of spinning a fluororubber composition containing at least one fluororubber selected from FKM and FFKM.
  • the manufacturing method including is preferable.
  • Step 1 Examples of the step 1 include an electrospinning method, a melt spinning method, a melt electrospinning method, and a spunbond method (melt blow method).
  • the electrospinning method and the 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 non-woven fabric or the like obtained by using the fiber tends to have a high porosity and a high specific surface area.
  • the electrospinning method is particularly preferable.
  • the obtained fibers may be formed on the collector, but in this case, a non-woven fabric may be formed on the collector. Therefore, one aspect of the method for producing this fiber is also a method for producing a non-woven fabric.
  • the fluororubber and, if necessary, a fluororubber composition containing a solvent are preferably used.
  • the proportion of the fluororubber contained in the fluororubber composition is, for example, 5 to 100% by mass, preferably 5 to 80% by mass, and more preferably 10 to 70% by mass.
  • the fluororubber may be used alone or in combination of two or more.
  • the solvent is not particularly limited as long as it can dissolve or disperse the fluorororubber, and for example, water, dimethylacetamide, dimethylformamide, tetrahydrofuran, methylpyrrolidone, xylene, acetone, methylethylketone, chloroform, ethylbenzene, cyclohexane, etc.
  • examples thereof include benzene, sulfolane, methanol, ethanol, phenol, pyridine, propylene carbonate, acetonitrile, trichloroethane, hexafluoroisopropanol and diethyl ether. These solvents may be used alone or in combination of two or more.
  • the solvent is contained in the fluororubber composition, for example, 0 to 90% by mass, preferably 10 to 90% by mass, and more preferably 20 to 80% by mass.
  • the fluororubber composition further contains other components such as other additives, surfactants, dispersants, charge adjusters, viscosity modifiers, fiber forming agents and the like which may be contained in the fiber. You may go out. Each of these other components may be used alone or in combination of two or more.
  • a fluororubber composition containing a cross-linking agent and / or a co-crosslinking agent may be used, and a fluororubber composition containing no cross-linking agent and / or a co-crosslinking agent may be used. May be used.
  • a cross-linking agent and / or a co-crosslinking agent is used, if the following step 2 is not performed, the cross-linking agent and the co-crosslinking agent may become impurities and the tensile properties of the fibers may deteriorate. Therefore, the following step 2 is performed. Is preferable.
  • cross-linking agent and the co-cross-linking agent examples include a cross-linking agent and a co-cross-linking agent similar to the cross-linking agent and the co-cross-linking agent described in the column of the other additives.
  • the amount of the cross-linking agent used with respect to 100 parts by mass of the fluororubber is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 10 parts by mass.
  • the amount of the co-crosslinking agent used with respect to 100 parts by mass of the fluororubber is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 10 parts by mass.
  • the fluororubber composition preferably contains one or more fiber-forming agents from the viewpoint of retaining the fluororubber in a fiber shape during spinning.
  • the fiber-forming agent is preferably an organic polymer having high solubility in a solvent, and for example, polyethylene oxide, polyethylene glycol, dextran, alginic acid, chitosan, starch, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, and poly. Examples include acrylamide, cellulose and polyvinyl alcohol.
  • the fiber forming agent the amount used depends on the viscosity of the solvent and the solubility in the solvent, but is, for example, 0.1 to 15% by mass, preferably 1 to 10% by mass in the fluororubber composition. be.
  • the applied voltage is preferably 1 to 100 kV, more preferably 5 to 50 kV, and even more preferably 10 to 40 kV.
  • the spinning distance is preferably 5 to 30 cm.
  • the discharge rate of the fluororubber composition is preferably 0.01 to 3 ml / min.
  • the tip diameter (outer diameter) of the spinning nozzle used for electric field spinning is preferably 0.1 to 2.0 mm, more preferably 0.2 to 1.6 mm.
  • the spinning atmosphere does not have to be particularly controlled, but the relative humidity is preferably 10 to 50% and the temperature is preferably 10 to 35 ° C.
  • a rotary collector or a flat plate can be used as the fiber collection collector.
  • the fibers ejected from the spinning nozzle are wound around the drum by rotating the drum, and a non-woven fabric in which the fibers are oriented in a certain direction can be obtained.
  • the rotation speed of the rotation collector is, for example, 50 to 5,000 rotations / minute.
  • a flat fiber collection collector By using a flat fiber collection collector, a non-woven fabric made of non-oriented fibers can be obtained.
  • melt spinning can be performed by melting the fluororubber composition with heat, extruding it from a spinneret (nozzle) to make it fibrous, and then cooling it.
  • the specific method of melt spinning is not particularly limited, and a known method can be used depending on the raw material used.
  • the fluororubber composition used for melt spinning is not particularly limited as long as it contains at least one fluororubber selected from FKM and FFKM, and is the same composition as the composition described in the column of electrospinning. You may.
  • Step 2 When producing the present fiber, only the step 1 may be performed, but the fiber shape (porous shape, non-woven fabric shape) obtained in the step 1 can be maintained for a long period of time, and the tensile strength and the tensile elastic modulus can be maintained. It is preferable to include the step 2 of cross-linking the fibers obtained in the above step 1 from the viewpoint that the fibers having improved tensile properties such as the above can be easily obtained. By going through such step 2, a fiber containing at least one selected from the crosslinked product of FKM and the crosslinked product of FFKM can be obtained.
  • the step 2 include a step of irradiating the fibers obtained in the step 1 with radiation (radiation crosslinking), a step of applying heat to the fibers obtained in the step 1 (thermal crosslinking), and the like.
  • radiation cross-linking is preferable because the cross-linking treatment can be performed in a short time and the fiber shape (porous shape, non-woven cloth shape) obtained in step 1 can be easily maintained.
  • the fiber obtained in step 1 may be a fiber immediately after being extruded from the nozzle or the like, or may be a fiber after being accumulated on a collector or the like.
  • the radiation examples include X-rays, gamma rays, electron beams, proton beams, neutron beams, heavy particle beams, alpha rays, and beta rays, and among these, electron beams are preferable.
  • the radiation to be irradiated may be one type alone or two or more types.
  • the radiation cross-linking method may be a conventionally known method, and examples of the conditions for irradiating the electron beam include the following conditions. It is desirable to irradiate the electron beam so that the absorbed dose is preferably 10 to 500 kGy, more preferably 20 to 300 kGy. When irradiating the 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 not easily inhibited and fibers having excellent mechanical properties can be easily obtained. ..
  • the heating conditions in the thermal crosslinking may be set according to the composition of the fluororubber composition to be used, and examples thereof include a heating temperature of 150 to 200 ° C. and a heating time of 1 to 24 hours. ..
  • the fluororubber non-woven fabric according to the embodiment of the present invention is not particularly limited as long as the present fiber is included, and examples thereof include a nonwoven fabric made of the present fiber.
  • the fiber constituting the non-woven fabric is a cross-linked body of FKM and / or a cross-linked body of FFKM from the viewpoint of being a non-woven fabric having excellent tensile properties such as shape retention, chemical resistance, tensile strength and tensile elastic modulus of the nonwoven fabric. It is preferable to include, and it is more preferable to include a crosslinked product of FKM.
  • the non-woven fabric can be used as a filter, a separator, a substrate, a base material, or the like for automobile members, aerospace members, chemical plants, semiconductor-related equipment, medical equipment, and the like. Further, according to one embodiment of the present invention, it is possible to maintain a desired shape such as a fiber shape or a porous shape for a long period of time, and to provide a flexible and stretchable nonwoven fabric, so that a flexible substrate (eg, flexible printed circuit board) can be provided. It can be suitably used as a material that requires flexibility, elasticity, etc., such as a substrate) and a wearable member. Further, according to one embodiment of the present invention, a nonwoven fabric having excellent breathability and water repellency and being hard to be soiled can be obtained, and from this point as well, it can be suitably used as a wearable member.
  • a desired shape such as a fiber shape or a porous shape for a long period of time
  • a flexible substrate eg, flexible printed circuit board
  • the porosity of the nonwoven fabric is not particularly limited, but is, for example, 0.1 to 95% by volume, preferably 30 to 90% by volume.
  • the basis weight of the nonwoven fabric is preferably 100 g / m 2 or less, more preferably 1 to 80 g / m 2 .
  • the thickness of the nonwoven fabric may be appropriately selected depending on the intended use of the nonwoven fabric, but is usually 5 ⁇ m to 1 mm, preferably 10 to 500 ⁇ m.
  • the non-woven fabric is made by accumulating the fibers in a sheet shape, and such a non-woven fabric and a woven fabric may be composed of a single layer or two or more layers having different materials and fiber diameters. good.
  • a step of forming the fibers by an electrospinning method or the like, and a step of accumulating the formed fibers into a sheet to form a nonwoven fabric are performed. It may be performed at the same time, or after performing the step of forming the fiber, the formed fiber is used, and the wet papermaking method, the water punch method, the chemical bond method, the thermal bond method, the spun bond method, the needle punch method, and the stitch bond are used. Depending on the method or the like, a step of accumulating in the form of a sheet to form a nonwoven fabric may be performed.
  • Example 1 Mooney viscosity at 121 ° C. measured according to FKM (Daiel G901H, Daikin Industries, Ltd., ASTM D 1646) with methyl ethyl ketone (special grade, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) so that the concentration is 20% by mass.
  • FKM Deniel G901H, Daikin Industries, Ltd., ASTM D 1646
  • methyl ethyl ketone special grade, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • a fluororubber composition in which (ML1 + 10): 53) was dissolved was prepared, and FKM fibers were placed on a collector to which aluminum foil was attached using an electrospinning device (manufactured by Mech Co., Ltd.) under the following conditions. Spinned directly.
  • the average fiber diameter of the obtained FKM fiber was about 1 ⁇ m.
  • the obtained FKM fiber was observed using an SEM (S-3400N, manufactured by Hitachi High-Technologies Corporation, the following SEM also used the same device) at magnifications of 500 times and 2000 times.
  • the upper left of FIG. 1 is an SEM image having a magnification of 500 times the obtained FKM fiber
  • the lower left of FIG. 1 is an SEM image of the obtained FKM fiber having a magnification of 2000 times. It can be said that the SEM image of FIG. 1 is an image of the obtained fiber and an image of the obtained non-woven fabric. It was found that the obtained FKM fiber maintained the same shape as immediately after spinning even after 24 hours had passed, and was excellent in shape stability.
  • FKM (Daiel G901H) was dissolved in methyl ethyl ketone (special grade, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) so that the concentration was 10% by mass, and TAIC (triallyl isocyanurate, manufactured by Mitsubishi Chemical Corporation) was dissolved therein.
  • a fluororubber composition by adding 4 parts by mass to 100 parts by mass of FKM, and use an electrospinning device (manufactured by MEC Corporation) on a collector to which aluminum foil is attached under the following conditions.
  • FKM fiber was directly spun.
  • the average fiber diameter of the obtained FKM fiber was about 1 ⁇ m.
  • the obtained FKM fiber showed the same SEM image as the fiber obtained in Example 1. It was found that the obtained FKM fiber maintained the same shape as immediately after spinning even after 24 hours had passed, and was excellent in shape stability.
  • Example 3 Mooney viscosity at 121 ° C. measured according to FKM (Daiel G902, Daikin Industries, Ltd., ASTM D 1646) with methyl ethyl ketone (special grade, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) so that the concentration is 20% by mass.
  • FKM Daiel G902, Daikin Industries, Ltd., ASTM D 1646) with methyl ethyl ketone (special grade, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) so that the concentration is 20% by mass.
  • a fluororubber composition in which (ML1 + 10): 21) was dissolved was prepared, and FKM fibers were placed on a collector to which aluminum foil was attached using an electrospinning device (manufactured by Mech Co., Ltd.) under the following conditions. Spinned directly.
  • the average fiber diameter of the obtained FKM fiber was about 2.3 ⁇ m.
  • the obtained FKM fibers immediately after spinning were observed using SEM at magnifications of 500 times and 2000 times.
  • the upper center of FIG. 1 is an SEM image having a magnification of 500 times the obtained FKM fiber
  • the lower center of FIG. 1 is an SEM image having a magnification of 2000 times the obtained FKM fiber. Since the obtained FKM fiber tended to lose its shape immediately after spinning, it was irradiated with an electron beam in the same manner as in Example 4 before the shape immediately after spinning collapsed.
  • a fluororubber composition was prepared in the same manner as in Example 1 except that FKM (Daiel G101, manufactured by Daikin Industries, Ltd., liquid rubber) was used so that the concentration was 10% by mass, and an electrospinning device (Co., Ltd.) was prepared. ) Made by MEC) was used to create an FKM-formed body on a collector to which aluminum foil was attached. However, since the solution sprayed on the collector became a spray, the obtained FKM-forming body did not have a fibrous shape.
  • the obtained FKM-forming body was observed using SEM at magnifications of 500 times and 2000 times.
  • the upper right of FIG. 1 is an SEM image with a magnification of 500 times the obtained FKM forming body, and the lower right of FIG. 1 is an SEM image with a magnification of 2000 times of the obtained FKM forming body.
  • Example 4 The FKM fiber obtained in Example 1 was irradiated with an electron beam (EB) using an EB device (CB250 / 30/20 mA manufactured by Iwasaki Electric Co., Ltd.). During this irradiation, the electron beam was irradiated at room temperature (21 ° C.) and under N 2 so that the absorbed dose was 100 kGy. The transport speed was 5 m / min.
  • EB electron beam
  • the fiber (nonwoven fabric) obtained by irradiating with an electron beam was observed using SEM at a magnification of 2000 times. The results are shown in the upper left of FIG. Moreover, the fiber after electron beam irradiation was immersed in methyl ethyl ketone for 2 days, and the fiber state was confirmed. The SEM image (magnification 2000 times) after being immersed in methyl ethyl ketone for 2 days is shown in the upper right of FIG. Although the fibers after immersion in methyl ethyl ketone were slightly swollen, it is considered that the fiber shape (porous shape, non-woven fabric shape) could be maintained even after immersion in methyl ethyl ketone due to cross-linking.
  • Example 5 The electron beam was irradiated in the same manner as in Example 4 except that the FKM fiber obtained in Example 2 was used.
  • the fiber (nonwoven fabric) obtained by irradiating with an electron beam was observed using SEM at a magnification of 2000 times. The results are shown in the lower left of FIG. Moreover, the fiber after electron beam irradiation was immersed in methyl ethyl ketone for 2 days, and the fiber state was confirmed.
  • the SEM image (magnification 2000 times) after being immersed in methyl ethyl ketone for 2 days is shown in the lower right of FIG. It is considered that the fiber shape (porous shape, non-woven fabric shape) could be maintained without swelling even after being immersed in the methyl ethyl ketone because the cross-linking proceeded more than the fiber obtained in Example 4.
  • Example 6 The electron beam was irradiated in the same manner as in Example 4 except that the FKM fiber obtained in Example 3 was used. When the fiber after electron beam irradiation was immersed in methyl ethyl ketone for 2 days and the fiber state was confirmed, the fiber shape (porous shape, non-woven fabric shape) could be maintained even after immersion in methyl ethyl ketone.
  • Example 7 In Example 1, a non-woven fabric having a thickness of about 38 ⁇ m was produced on a collector to which aluminum foil was attached in the same manner as in Example 1 except that the spinning time was set to 1 hour.
  • Example 8 The non-woven fabric obtained in Example 7 was irradiated with an electron beam (EB) using an EB device (CB250 / 30/20 mA manufactured by Iwasaki Electric Co., Ltd.). During this irradiation, the electron beam was irradiated at room temperature (21 ° C.) and under N 2 so that the absorbed dose was 100 kGy. The transport speed was 5 m / min.
  • EB electron beam
  • Example 9 In Example 3, a non-woven fabric was produced on a collector to which aluminum foil was attached in the same manner as in Example 3 except that the spinning time was set to 1 hour. The prepared nonwoven fabric was irradiated with an electron beam in the same manner as in Example 8.
  • ⁇ Tensile test evaluation> After punching each of the non-woven fabrics obtained in Examples 7 to 9 into a JIS dumbbell-shaped No. 3 shape, a tensile tester (small desktop tester, manufactured by Shimadzu Corporation) was used at a speed of 1.0 mm / sec. A tensile test was performed at. From the stress and elongation at that time, the tensile strength and the tensile elastic modulus were calculated.
  • the tensile strength ⁇ max is the maximum tensile stress applied during the tensile test, and was calculated from the cross-sectional area A with respect to the maximum load F max by the following equation.
  • Example 10 In Example 2, a non-woven fabric having a thickness of about 38 ⁇ m was produced on a collector to which aluminum foil was attached in the same manner as in Example 2 except that the spinning time was set to 1 hour.
  • Example 11 The non-woven fabric obtained in Example 10 was irradiated with an electron beam (EB) using an EB device (CB250 / 30/20 mA manufactured by Iwasaki Electric Co., Ltd.). During this irradiation, the electron beam was irradiated at room temperature (21 ° C.) and under N 2 so that the absorbed dose was 100 kGy. The transport speed was 5 m / min.
  • EB electron beam
  • the cross-linking treatment can be performed while maintaining the porous structure, and from the comparison between Examples 10 and 11 in Table 2, the tensile strength is improved by going through the cross-linking step. Further, from Table 2, it can be seen that when the co-crosslinking agent (TAIC) was blended, the tensile elastic modulus (rubber hardness) could be improved by performing the cross-linking step. From the above, it can be said that according to one embodiment of the present invention, a flexible and stretchable porous nonwoven fabric structure containing fluororubber fibers could be produced.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nonwoven Fabrics (AREA)
PCT/JP2021/019563 2020-06-05 2021-05-24 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 Ceased WO2021246218A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2022528754A JP7772696B2 (ja) 2020-06-05 2021-05-24 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

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020098633 2020-06-05
JP2020-098633 2020-06-05

Publications (1)

Publication Number Publication Date
WO2021246218A1 true WO2021246218A1 (ja) 2021-12-09

Family

ID=78830963

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/019563 Ceased WO2021246218A1 (ja) 2020-06-05 2021-05-24 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

Country Status (3)

Country Link
JP (1) JP7772696B2 (https=)
TW (1) TWI869598B (https=)
WO (1) WO2021246218A1 (https=)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022210267A1 (ja) * 2021-03-30 2022-10-06 株式会社バルカー 機能材料および機能材料の製造方法
JP2023143118A (ja) * 2022-03-25 2023-10-06 株式会社バルカー フッ素ゴムシートの製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115902062B (zh) * 2022-11-23 2025-02-25 山西北化关铝化工有限公司 一种cg-k(2)炸药中组分的检测方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5959909A (ja) * 1982-09-29 1984-04-05 Daikin Ind Ltd ゴム弾性フイラメント
JPS59162503A (ja) * 1983-03-07 1984-09-13 Sumitomo Chem Co Ltd 光伝送繊維
JP2002309478A (ja) * 2001-04-13 2002-10-23 Hitachi Cable Ltd 架橋ｐｔｆｅ繊維の製造方法および架橋ｐｔｆｅ繊維から成る成形品。
CN103741230A (zh) * 2014-01-08 2014-04-23 青岛科技大学 一种交联橡胶纳米纤维材料及其制法和用途
JP2014511443A (ja) * 2011-03-09 2014-05-15 ボード・オブ・リージエンツ，ザ・ユニバーシテイ・オブ・テキサス・システム 繊維の製造のための装置及び方法
WO2015083546A1 (ja) * 2013-12-03 2015-06-11 日本バルカー工業株式会社 電気化学素子用複合膜
US20150209691A1 (en) * 2007-08-01 2015-07-30 Donaldson Company, Inc. Fluoropolymer fine fiber

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010039579A1 (en) * 2008-09-30 2010-04-08 Exxonmobil Chemical Patents Inc. Extensible nonwoven facing layer for elastic multilayer fabrics
CN106564255A (zh) * 2009-02-27 2017-04-19 埃克森美孚化学专利公司 具有非弹性区的双轴弹性非织造层压体

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5959909A (ja) * 1982-09-29 1984-04-05 Daikin Ind Ltd ゴム弾性フイラメント
JPS59162503A (ja) * 1983-03-07 1984-09-13 Sumitomo Chem Co Ltd 光伝送繊維
JP2002309478A (ja) * 2001-04-13 2002-10-23 Hitachi Cable Ltd 架橋ｐｔｆｅ繊維の製造方法および架橋ｐｔｆｅ繊維から成る成形品。
US20150209691A1 (en) * 2007-08-01 2015-07-30 Donaldson Company, Inc. Fluoropolymer fine fiber
JP2014511443A (ja) * 2011-03-09 2014-05-15 ボード・オブ・リージエンツ，ザ・ユニバーシテイ・オブ・テキサス・システム 繊維の製造のための装置及び方法
WO2015083546A1 (ja) * 2013-12-03 2015-06-11 日本バルカー工業株式会社 電気化学素子用複合膜
CN103741230A (zh) * 2014-01-08 2014-04-23 青岛科技大学 一种交联橡胶纳米纤维材料及其制法和用途

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022210267A1 (ja) * 2021-03-30 2022-10-06 株式会社バルカー 機能材料および機能材料の製造方法
JP2023143118A (ja) * 2022-03-25 2023-10-06 株式会社バルカー フッ素ゴムシートの製造方法

Also Published As

Publication number Publication date
TW202204706A (zh) 2022-02-01
JP7772696B2 (ja) 2025-11-18
JPWO2021246218A1 (https=) 2021-12-09
TWI869598B (zh) 2025-01-11

Similar Documents

Publication Publication Date Title
JP7772696B2 (ja) 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
JP6218723B2 (ja) 二軸延伸多孔質膜
JP7041900B2 (ja) ニトリルオキシド化合物
US10688448B2 (en) Porous body, polymer electrolyte membrane, filter material for filter, and filter unit
US10113041B2 (en) Film and method for producing same
CN103261314A (zh) 聚四氟乙烯混合物
WO2018181904A1 (ja) フルオロポリマーの製造方法、重合用界面活性剤及び界面活性剤の使用
KR20200128118A (ko) 전파 흡수 재료 및 전파 흡수 시트
WO2019156175A1 (ja) フルオロポリマーの製造方法、重合用界面活性剤、界面活性剤の使用及び組成物
JP2015086364A (ja) 成形品およびその製造方法ならびに電線およびその製造方法
US10144792B2 (en) Method for producing electric wire, method for producing molded artile, and method for producing resin material containing modified fluororesin
CN110709465B (zh) 含氟弹性体组合物及其成型品
WO2022026136A1 (en) Method of producing carbon molecular sieve membranes
JP2017504157A (ja) 導電性炭素粉末、その製造方法及びその使用
JP5429008B2 (ja) 組成物、ペレット、樹脂成形品及び電線、並びに、組成物の製造方法
JP2010037365A (ja) 含フッ素ポリマーの製造方法。
WO2022210267A1 (ja) 機能材料および機能材料の製造方法
JP2023143118A (ja) フッ素ゴムシートの製造方法
JP3929091B2 (ja) 架橋性フッ化ビニリデン重合体組成物、該組成物の架橋方法及び造形品
WO2019057682A1 (en) POROUS MEMBRANE AND METHOD FOR MANUFACTURING THE SAME
JP5261933B2 (ja) オキシメチレン複合繊維
JP2015096577A (ja) 電線被覆材用樹脂組成物および電線
KR20240074818A (ko) 조성물, 회로 기판, 및, 조성물의 제조 방법
JP5594338B2 (ja) 全フッ素化飽和炭化水素及び含フッ素界面活性剤を含む組成物
JP6447259B2 (ja) ポリアリーレンスルフィド樹脂繊維集合体およびその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21817398

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022528754

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21817398

Country of ref document: EP

Kind code of ref document: A1