WO2016088692A1 - Procédé de fabrication de filtre électret - Google Patents

Procédé de fabrication de filtre électret Download PDF

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Publication number
WO2016088692A1
WO2016088692A1 PCT/JP2015/083522 JP2015083522W WO2016088692A1 WO 2016088692 A1 WO2016088692 A1 WO 2016088692A1 JP 2015083522 W JP2015083522 W JP 2015083522W WO 2016088692 A1 WO2016088692 A1 WO 2016088692A1
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Prior art keywords
fluorine
particles
electret filter
filter
carrier
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PCT/JP2015/083522
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English (en)
Japanese (ja)
Inventor
北川　義幸
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東洋紡株式会社
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Priority to JP2016562431A priority Critical patent/JP6743706B2/ja
Publication of WO2016088692A1 publication Critical patent/WO2016088692A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C3/00—Separating dispersed particles from gases or vapour, e.g. air, by electrostatic effect
    • B03C3/28—Plant or installations without electricity supply, e.g. using electrets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material

Definitions

  • the present invention relates to a method for manufacturing an electret filter.
  • porous filters are used for dust collection, protection, ventilation, etc. in dust masks, various air conditioning elements, air purifiers, cabin filters, and the like.
  • the fiber layer filter made of a fibrous material has a high porosity, has the advantages of long life and low ventilation resistance, and is widely used.
  • particles are captured on the fiber by a mechanical collection mechanism such as contact adhesion, diffusion, inertial collision, and the like. These mechanisms vary depending on the physical properties of the particles, the fiber diameter, the passing air speed of the particles, etc., but in practical use environments, the filter particles are used when the aerodynamic equivalent diameter is about 0.1 to 1.0 ⁇ m. It is known that the collection efficiency is the lowest.
  • a method using electric attractive force in combination is known.
  • a method of applying a charge to particles to be collected a method of applying a charge to a filter, or a combination of both methods are known.
  • a method for applying a charge to a filter a method in which a filter is disposed between electrodes and dielectric polarization is performed during ventilation, and a method in which a long-life electrostatic charge is applied to an insulating material are known. In particular, in the latter case, energy such as an external power source is not required. Therefore, a filter containing such an insulating material is widely used as an electret filter.
  • the fiber layer filter can be electretized and has moisture resistance and stability. A material having excellent heat stability is used.
  • the electret filter described above has a drawback that electrostatic attraction decreases as the collection of particles proceeds. Especially when collecting oil mist with a small surface tension, the oil mist covers the entire fiber surface thinly. As a result, the loss of electric charge is significantly promoted.
  • Polyolefin, polyester, polycarbonate, phenol resin, etc. with excellent charge stability are used as materials for general electret filters.
  • polypropylene, polyethylene, polymethylpentene, which have the smallest surface tension are used.
  • polyolefin resins such as poly- ⁇ -olefin (PAO) and dioctyl phthalate (DOP)
  • PAO poly- ⁇ -olefin
  • DOP dioctyl phthalate
  • the oil repellency is improved by lowering the surface tension of the fibrous material constituting the filter, and the spread of the mist-like particles on the fiber surface and the diffusion into the fiber is suppressed.
  • a method of improving particle collection efficiency when oil mist is added to a filter by reducing the disappearance of the above charge is known.
  • a method of mixing an additive having a perfluoro group with a resin for example, Patent Document 1
  • a method of melt spinning a thermoplastic fluororesin for example, Patent Document 2 and Patent Document 3
  • a perfluoro group A method of coating the surface with an emulsion processing agent for example, Patent Document 4
  • a method of introducing fluorine atoms into a polymer constituting a filter by replacing constituent elements by fluorine gas treatment or plasma treatment for example, Patent Document 5
  • a technique is known in which the surface tension of an electret filter is reduced and oil mist resistance is increased while maintaining charge stability by such a method.
  • oil repellency the effect of oil repellency by lowering the surface tension of the material
  • oil mist resistance the effect of suppressing reduction in the particle collection efficiency of the material when oil mist is added
  • oil repellency in the present invention means the effect of suppressing the spread of the liquid on the surface of the material by lowering the surface tension of the material, and acting on water having a large surface tension value in view of the principle of wetting. (Water repellency) is also included.
  • fluorinated resins and fluorinated low-molecular additives are not suitable for melt spinning in environments where the temperature exceeds 320 ° C. Unsuitable.
  • the fluorine atom introduction method by fluorine gas treatment or plasma treatment needs to prevent leakage of fluorine gas, and it is necessary to strictly manage oxygen and water content in order to suppress the increase in hydrophilicity due to residual oxygen. Yes, special equipment with high airtightness is required.
  • PFOS perfluorooctane sulfonic acid
  • PFOA perfluorooctanoic acid
  • the processing agent loses crystallinity, and the processing agent itself does not have electret properties, and even if it has a low adhesion amount, There is a problem that the electret property of the fiber material used as a material is significantly inhibited.
  • Patent Document 6 a fluorine-based resin that imparts solubility and thermoplasticity by amorphization and has both electret and coating properties is also known, but it is necessary to use a special monomer as the main skeleton. There is a problem that the manufacturing cost is remarkably increased.
  • the present invention has been given as an object to provide an electret filter that can be manufactured by a low-cost and simple method and has oil repellency, oil mist resistance, and charge stability.
  • the present inventor uses a fluorine-containing polymer obtained from a monomer component containing a fluorine-containing polycyclic compound, or a monomer having a fluorine-containing alkyl group or fluorine-containing alkylene group having 7 or less carbon atoms, to provide oil repellency and oil resistance.
  • the inventors have found a production method for obtaining an electret filter having excellent mist properties and charge stability.
  • a method for producing an electret filter in which fluorine-containing particles substantially free of metal and metal oxide are attached to a carrier using a liquid phase or a gas phase in which the fluorine-containing particles are dispersed.
  • a production method including a step of attaching the fluorine-containing particles to the carrier.
  • the fluorine-containing particles are made of a fluorine-containing polymer obtained from a fluorine-containing polycyclic compound, or a monomer component containing a fluorine-containing olefin or a (meth) acrylate having a fluorine-containing side chain, and the fluorine-containing polycyclic compound and the above-mentioned
  • the fluorine-containing polymer is characterized in that a fluorine telomer having 8 or more carbon atoms and all hydrogens substituted with carbon is not generated by hydrolysis.
  • the melting point or glass transition temperature of the fluorine-containing particles is 40 ° C. or higher.
  • the particle size of the fluorine-containing particles is preferably 1 nm or more and 500 nm or less.
  • the present invention also includes an electret filter manufactured by the above manufacturing method.
  • an electret filter having excellent oil repellency, oil mist resistance, and charge stability can be obtained.
  • the electret filter produced according to the present invention is obtained by attaching fluorine-containing particles substantially free of metal and metal oxide to a carrier.
  • the carrier used in the present invention is not particularly limited as long as it has desired characteristics, but it is preferable to use a synthetic resin having a high electrical resistance from the viewpoint of the degree of freedom in shape and the charge stability of the electret filter.
  • Specific materials include polyester, polycarbonate, polyamide, polyolefin, cyclic olefin, polyvinyl chloride, polyvinylidene chloride, and the like, and polyolefin materials such as polyethylene, polybutene, polypropylene, polymethylpentene, and cyclic olefin, and polystyrene materials are preferable. .
  • an electret filter having high electrical resistance, a good balance of hydrophobicity, moldability, etc., and excellent particle collection efficiency, that is, an electret filter excellent in practicality is obtained. be able to.
  • Synthetic resins containing fluorine atoms include, for example, polytetrafluoroethylene (PTFE), perfluoroethylene propene copolymer (FEP), perfluoroalkoxyalkane (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), polychlorotrifluoro Examples thereof include ethylene (PCTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), and PTFE, FEP, PFA, and ETFE are more preferable from the viewpoint of oil repellency.
  • PTFE polytetrafluoroethylene
  • FEP perfluoroethylene propene copolymer
  • PFA perfluoroalkoxyalkane
  • ETFE ethylene-tetrafluoroethylene copolymer
  • PCTFE polychlorotrifluoro Examples thereof include ethylene (PC
  • a known compounding agent may be added to the resin in order to suppress the deterioration of the resin itself and increase the charge stability in the carrier.
  • the compounding agent include various metal salts, antioxidants, light stabilizers and the like.
  • the carrier in order to suppress deterioration of the resin itself and increase charge stability in the carrier, the carrier may be formed using a plurality of different materials. For example, two or more different resin components are mixed.
  • a compatible or incompatible blend polymer, ionomer, maleic acid-modified polyolefin, hindered phenol resin, hindered amine resin, or the like can be used.
  • the carrier used in the present invention may be a woven fabric shape, a nonwoven fabric shape, a cotton shape, or the like that is obtained by molding a fibrous material obtained by a known technique into an appropriate shape and thickness according to the application, From the viewpoint of particle removal performance, a nonwoven fabric is preferable.
  • the method for forming the nonwoven carrier is not particularly limited.
  • the melt blown method, the wet method, the dry method, the spunbond method, the flash spinning method, the electrospinning method, the force spinning method, the supersonic stretching method Known methods such as a composite fiber splitting method may be mentioned.
  • the present invention uses a melt blown method, an electrospinning method, a force spinning method, or supersonic stretching. The method is preferably adopted. Further, from the viewpoint of not requiring treatment of the residual solvent, it is preferable to employ a melt blown method, a melt electrospinning method, a melt force spinning method, or a supersonic stretching method.
  • the fibrous material in the present invention is produced by a single production method or synthetic resin, the type of resin is the same, but the production method, fiber diameter, etc. may be produced from different synthetic resins. Alternatively, it may be made from two or more synthetic resins.
  • the diameter of the fiber used in the carrier of the present invention is preferably 0.001 to 100 ⁇ m, more preferably 0.005 to 20 ⁇ m, still more preferably 0.01 to 10 ⁇ m, and particularly preferably 0.02. To 5 ⁇ m, and most preferably 0.03 to 3 ⁇ m. If the fiber diameter is within the above range, the air ventilation resistance in the carrier can be reduced while increasing the collection efficiency. When the fiber diameter is thinner than 0.001 ⁇ m, it is difficult to give a charge to the carrier, and when the fiber diameter is thicker than 100 ⁇ m, the collection efficiency may be lowered. There is a large decrease in efficiency in various performances.
  • the electret filter of the present invention is characterized by using fluorine-containing particles containing fluorine atoms for imparting water repellency and oil repellency to at least a part of the surface of the carrier.
  • the fluorine-containing particles are made of a fluorine-containing polymer obtained from a monomer component containing a fluorine-containing polycyclic compound, or a fluorine-containing olefin or a (meth) acrylate having a fluorine-containing side chain.
  • the fluorine-containing polymer and the fluorine-containing polycyclic compound have a carbon number of 8 or more and all hydrogen is replaced with carbon by hydrolysis. It is characterized in that no fluorine telomer is generated.
  • the fluorine-containing polycyclic compound preferably has a fluorine substitution rate of hydrogen atoms of 80% or more, more preferably 90% or more, and most preferably 95% or more.
  • the fluorine-containing polycyclic compound has a melting point of 40 ° C. or higher, preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably. It is 100 ° C or higher.
  • a fluorinated graphite, a fluorinated fullerene, a fluorinated carbon nanotube or the like is preferable for a three-dimensional structure, and a fluorinated graphene or the like is preferable for a planar structure.
  • the fluorine-containing polymer has a glass transition temperature of 40 ° C. or higher, preferably 60 ° C. or higher, more preferably 80, in order to suppress charge stability inhibition due to adhesion between particles or flow. It is 100 degreeC or more more preferably.
  • a (meth) acrylic acid polymer having a perfluoro structure of C 7 or less (preferably C 6 or less) at least in the side chain, soluble in fluorine solvents
  • modified PTFE examples thereof include modified PTFE.
  • halogen atoms are introduced into the main chain of the polymer, rigid short-chain methyl methacrylate, Making it a copolymer with monomers such as fluoromethyl methacrylate, highly sterically hindered styrene-containing olefins, dicyclopentenyl group-containing olefins, dicyclopentanyl group-containing olefins, and introducing crystallinity polymerization This is a preferable method.
  • fluorine-containing (meth) acrylic acid-based polymers include (co) polymers containing fluorine-containing olefins.
  • fluorine-containing (meth) acrylic acid include fluoroalkyls.
  • Co polymer containing (meth) acrylate having a group in the side chain.
  • the fluorine-containing particles are preferably not a coating on a metal and a metal oxide, and the fluorine-containing particles are not a mixture with a metal and a metal oxide. Is preferred. In 100% by mass of fluorine-containing particles, the content of metal and metal oxide is preferably 10% by mass or less, more preferably 5% by mass or less, and 0% by mass (including metal and metal oxide at all). More preferably).
  • the fluorine-containing particles contain a small amount of surfactant or no surfactant.
  • the content of the surfactant is preferably 25% by mass or less, more preferably 10% by mass or less, and 0% by mass (the surfactant is completely contained). More preferably). Particles containing a surfactant exceeding the above range may impair the water / oil repellency and charge stability of the particles themselves and the substrate.
  • the fluorine-containing olefin preferably has a perfluoroalkyl group and / or a perfluoroalkylene group.
  • the perfluoroalkyl group and / or the perfluoroalkylene group preferably has 1 to 7 carbon atoms, more preferably a perfluoroalkyl group having 4 to 6 carbon atoms at the end of the side chain. More preferably.
  • the fluorine-containing (meth) acrylate preferably has a (meth) acryloyl group having a trifluoromethyl group located at the terminal.
  • the fluorine-containing polymer may contain oxygen, silicon, nitrogen atoms and the like as a linking group, but more preferably has a structure consisting of only hydrogen, fluorine, and carbon atoms.
  • a structure consisting of only hydrogen, fluorine, and carbon atoms since there are no unpaired atoms and asymmetric polar components, surface tension and hygroscopicity are reduced, and as a result, oil resistance and electret properties are improved.
  • the fluorine-containing polymer has one or more aromatic hydrocarbon groups and linear / branched / cycloaliphatic hydrocarbon groups as spacers with the main chain.
  • ⁇ -chloro (meth) acrylate is used as the main chain, a chlorine atom having a large steric hindrance can be incorporated into the main chain, so that the polymer content can be maintained while maintaining a high content ratio of the fluorine-containing monomer. As a result, a high glass transition temperature can be obtained, and charge stability and oil repellency can be easily improved.
  • the (meth) acrylate having a fluorine-containing side chain of the present invention it is preferable to use a monomer having a short fluorine-containing side chain having 1 to 7 carbon atoms.
  • a (meth) acrylate having a linear aliphatic hydrocarbon group having 12 to 30 carbon atoms as a monomer to be copolymerized with these fluorine-containing monomers. Examples include lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.
  • a (meth) acrylate having a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group can be used.
  • examples include cycloalkyl groups such as cyclohexyl group; polycyclic aliphatic hydrocarbon groups having 7 to 20 carbon atoms such as norbornyl group, bornyl group, isobornyl group, adamantyl group; phenyl group, naphthyl group, benzyl group, etc.
  • (Meth) acrylate having an aromatic hydrocarbon group is
  • the resulting copolymer has a high melting point or glass transition temperature, and further blocks the ester group and reduces molecular mobility, so that it has electret properties. The stability of is improved.
  • Examples of the (meth) acrylate include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Examples include tricyclodecanyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, and 2-t-butylphenyl (meth) acrylate.
  • a homopolymer having a cyclic aliphatic hydrocarbon group is characterized by a significantly higher glass transition temperature than a homopolymer having a linear aliphatic hydrocarbon group, while maintaining a high content ratio of the fluorine-containing monomer. As a polymer, a high glass transition temperature can be obtained.
  • a monomer having a halogenated olefin, a functional group having crosslinkability, a hindered phenol structure or a hindered amine structure imparting an antioxidant action and charge stability can also be used.
  • the halogenated olefin is preferably used as long as it has 2 or more carbon atoms. Examples thereof include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, vinylidene bromide, and vinylidene iodide.
  • the copolymerization ratio of the fluorine-containing monomer and the non-fluorine monomer is preferably in the range of 100: 0 to 10:90, more preferably 100: 0 to 20:80, and still more preferably 100: 0. ⁇ 30: 70.
  • fluorine-containing particles having a particle size of 0.1 nm to 500 nm are attached to the carrier. It is more preferably 0.5 nm or more and 300 nm or less, further preferably 1 nm or more and 200 nm or less, and most preferably 2 nm or more and 100 nm or less.
  • the particle size is larger than 500 nm, it is difficult to achieve uniformity in particle size at the time of dispersion, and the coating layer thickness is likely to be excessive, making handling difficult.
  • the floating oil mist to be collected is usually 500 nm or less, it is difficult to impart oil repellency due to unevenness.
  • the particle size is less than 0.1 nm, it is not suitable as a coating application in terms of solubility, melting point and vapor pressure, and the oil repellency, durability stability and electret stability may be inferior.
  • the diameter ratio of the fibrous material to the particle is important, and the value obtained by dividing the fiber diameter by the particle diameter (fiber diameter / particle diameter) Is preferably 1 or more, more preferably 10 or more, and most preferably 100 or more. Further, it is generally known that the smaller the fiber diameter is, the more the filtration characteristics (capture efficiency per unit ventilation resistance) are improved, and the increase in the fiber diameter due to the coating layer is suppressed.
  • a method for adjusting the particle size (1) a method of adjusting the particle size at the time of polymerization by performing emulsion polymerization or suspension polymerization, and (2) pulverizing the fluorine-containing polymer by physical action such as impact and friction. (3) A method in which a fluorine-containing polymer is dissolved in a fluorine-based solvent, supercritical carbon dioxide or the like, and then sprayed onto a carrier, and (4) a fluorine-containing polymer in a fluorine-based solvent, supercritical carbon dioxide, or the like (5) A method of spraying onto a carrier after heating to a temperature higher than the melting point, (6) Transpiration and condensation due to changes in pressure and temperature. The method etc.
  • a preferable method can be used according to the target particle diameter.
  • particles obtained by emulsion polymerization, suspension polymerization, reprecipitation, etc. they may be attached to the carrier in a solid-liquid mixed state, or may be taken out as particles through a drying step.
  • a fluorine-containing polymer can be produced by a known method using the above monomer.
  • wet or dry pulverizers As a method of pulverizing by physical action, various types of wet or dry pulverizers can be used. Specifically, a ball mill, a bead mill, a jet mill, a homogenizer, and the like can be exemplified. It can also be suspended.
  • water, a hydrocarbon organic solvent, a halogen organic solvent, or the like is preferably used as the dispersion medium, and two or more kinds of dispersion media can be mixed and used.
  • an organic solvent is used as the dispersion medium, the permeability and the uniformity of the coating can be improved by the affinity with the synthetic resin used as the carrier.
  • various surfactants can also be used. Since the surfactant inhibits the expression of oil repellency and the stability of the electret, it is preferable to finally remove and / or inactivate the surfactant from the fluorine-containing particles.
  • a method of evaporating the surfactant by heat treatment before or after adhesion a method of removing the surfactant from the fluorine-containing particles by thermal decomposition or oxidative decomposition, and removing the surfactant from the fluorine-containing particles by washing with water or a solvent.
  • a method of sealing an ionic functional group with a transition metal ion or a reactive organic substance can be used.
  • a method of dispersing fluorine-containing particles without using a surfactant it is preferable to use a fluorine-containing solvent as a dispersion medium.
  • Examples of the method for atomizing by spraying include airless or air pressure spraying, ultrasonic atomization, Ruskin nozzle, collision, electrostatic spraying, and the like.
  • the particle diameter proportional to the solution concentration can be easily adjusted by using a solution or a pre-particulate suspension.
  • a method for spraying a solution or suspension is suitable, and it may be attached in any of a solution state, a semi-transpiration state, and a solidified state. Absent.
  • a method of making particles by transpiration a method in which a fluorine-containing material is vaporized by heating or reduced pressure and then deposited directly on the surface of the carrier by cooling or pressurizing, or a method of making particles in gas adhere to the surface of the carrier. Can be used.
  • a step (liquid phase method or vapor phase method) of attaching fluorine-containing particles to a carrier using a liquid phase or a gas phase in which fluorine-containing particles are dispersed is included.
  • the carrier is used for a filter, if the particles are attached to the carrier by a liquid phase method or a gas phase method, the carrier can be processed without using a surfactant, and the particle collecting property of the carrier itself can be utilized.
  • the electret filter of the present invention at least one of the carrier and the fluorine-containing particles is electretized, that is, an electrostatic charge is imparted.
  • the electretization method is not particularly limited as long as desired characteristics can be obtained at the time of use, and may be before or after supporting the fluorine-containing particles. In the former case, there is an advantage in adhesion and processing by attracting the fluorine-containing powder by electrostatic attraction, and in the latter case, the electric lines of force of the carrier are not shielded, so that the electret effect can be expressed more. .
  • the electretization method includes polarization by high voltage, collision of charged ions, method by electric action such as injection of charged particles, method by interaction with solids such as friction and collision, method utilizing contact and collision with liquid
  • a known method can be preferably used.
  • a method utilizing contact with a liquid or friction is more preferable. When this method is used, electretization can be performed without increasing the oxidation product having polarity.
  • oil repellency of the electret filter of the present invention a drop of a test liquid used in the AATCC-118 method or a liquid mixture for a wet tension test used in JIS K 6768 is dropped and brought into contact for 30 seconds.
  • the tension of the filter surface is measured based on the presence or absence of penetration of oil, and the smaller the surface tension required for penetration, the higher the oil repellency.
  • the oil repellency of the electret filter of the present invention can be adjusted according to the required properties (waterproof, antifouling, water repellent, oil repellent, etc.), but was measured using the above liquid.
  • the surface tension is at least lower than the unprocessed product (for example, the surface tension of polypropylene obtained by the melt blown method is 36 mN / m). Specifically, it is more preferably 31 mN / m or less, further preferably 29 mN / m or less, particularly preferably 27 mN / m or less, and most preferably 25 mN / m or less.
  • the electret filter of the present invention is preferably used by further laminating a fiber layer (hereinafter referred to as a liquid absorbing layer) having an oil absorbing function or a water absorbing function.
  • a fiber layer hereinafter referred to as a liquid absorbing layer
  • a non-fluorine material when used as a carrier, it has an oil absorbing function even when a general-purpose resin such as polyethylene or polypropylene is laminated.
  • a liquid-absorbing layer having a liquid-absorbing function such as oil absorption and water absorption
  • the liquid droplets generated by oil repellency can be prevented from dripping, the liquid droplets can be transferred from the surface of the electret filter and diffused to Loss of electret property and increase in ventilation resistance can be suppressed.
  • the material of the liquid-absorbing layer is not particularly limited as long as it absorbs liquid droplets, but is a fiber sheet material composed of polypropylene, polyethylene, polystyrene, polyamide, polyacrylonitrile, polyester, polycarbonate, cellulose, rayon, activated carbon, zeolite
  • a sheet material containing a porous material such as pulp in the gap or processed into a surface is preferable. More preferably, it is an olefin fiber sheet material such as polypropylene, polyethylene, polystyrene, or the like, or a fiber sheet material made of polyester, and more preferably a fiber sheet material made of polypropylene.
  • the fibers constituting the liquid absorption layer preferably have a diameter of 0.005 to 100 ⁇ m, more preferably 0.01 to 20 ⁇ m, still more preferably 0.5 to 10 ⁇ m, and 1 to 5 ⁇ m. Most preferably it is.
  • the fibers used in the liquid absorbing layer can be used alone or in combination of two or more, and the material can be selected from the viewpoints of collecting coarse particles and ventilation resistance.
  • the material used for the liquid absorbing layer may be a non-electret material or an electret material, but is preferably an electret material.
  • the production method of the liquid absorbing layer is not particularly limited as long as the desired properties can be obtained, but it is not limited by the thermal bond method, the spun bond method, the spun lace method, the melt electro spinning method, the solution electro spinning method, the force spinning method, or the like. It can be produced using a sheet material.
  • the electret filter of the present invention can be used in combination with layers such as a prefilter layer, a fiber protective layer, a functional fiber layer, and a reinforcing layer, if necessary. These layers may be layers formed by adhering the fluorine-containing polymer used in the present invention.
  • Examples of the prefilter layer and the fiber protective layer include a spunbond nonwoven fabric, a thermal bond nonwoven fabric, and urethane foam.
  • Examples of the functional fiber layer include antibacterial, antiviral, colored fiber layers for identification and design purposes.
  • Examples of the reinforcing layer include a thermal bond nonwoven fabric and various nets.
  • the electret filter of the present invention can be widely used due to functions such as dust collection, protection, ventilation, antifouling and waterproofing.
  • the filter of the present invention can be suitably used as, for example, a dust mask, various air conditioning elements, an air purifier, a cabin filter, and a filter for the purpose of protecting various devices.
  • the glass transition temperature of the particles is measured in accordance with JIS K 7121. Specifically, 10 mg of a sample is put in a measurement closed pan, and the temperature rise rate is 20 ° C./min. The midpoint glass transition temperature measured using a differential scanning calorimeter manufactured by TA Instruments was used as the glass transition temperature.
  • the melting point of the particles is measured in accordance with JIS K 7121. Specifically, 5 mg of a sample is put in a measurement airtight pan, and the temperature is increased by 10 ° C / min. Using a differential scanning calorimeter manufactured by KK, the peak temperature measured on an airtight closed pan was determined as the melting point by confirming the presence of a recrystallization peak.
  • the surface tension of the test liquid with the smallest surface tension that was not completely absorbed was measured according to JIS K 6768.
  • the oil repellency was measured with a wet tension test solution. As a result of sequential measurement, if there is a difference between the front and back surfaces of the test material, the surface tension with the smaller surface tension is defined as the oil repellency (the same applies to the oil repellency at AATCC 118). ). Further, when the test solution of 25 mN / m was non-penetrating, there was no penetrating test solution, so the test result was set to 25 mN / m.
  • Evaluation particle Emery 3004 (PAO) in an equilibrium charged state Mode diameter 0.184 ⁇ m Ventilation speed: 5 cm / sec (6 L / min) Concentration: 100 mg / m 3
  • Efficiency calculation Concentration evaluation before and after passing through the filter by the light scattering concentration method
  • the collection efficiency of particles having a particle size of 0.3 to 0.5 ⁇ m by the light scattering concentration method is 0.3 to 0.5 ⁇ m by the light scattering counter. It has been confirmed that it almost coincides with the value of the particle collection efficiency of 0.5 ⁇ m.
  • Evaluation particle Solid NaCl in an equilibrium charged state (generated from 2% by mass NaCl water) mode particle size 0.075 ⁇ m Ventilation speed: 5 cm / sec (6 L / min) Concentration: 200 mg / m 3
  • Efficiency calculation Concentration evaluation before and after passing through the filter by the light scattering concentration method
  • the numerical value of the filter tester mode (efficiency measurement mode) for one cycle is set with a value of 20 seconds set as the time for the upper and lower detectors to equilibrate. Using.
  • a dispersion was prepared by dispersing n-C 20 F 42 in perfluorohexane so that L16828 (n-C 20 F 42 : melting point 167 ° C.) manufactured by Alfa Aesar was 1% by mass.
  • a polypropylene nonwoven fabric hereinafter simply referred to as a polypropylene nonwoven fabric
  • the particles are polypropylene. 0.54 g / m 2 adhered to the nonwoven fabric as a solid content.
  • DMA Differential electric mobility analyzer
  • CNC condensing nucleus particle counter
  • Example 2 A dispersion was prepared by dispersing n-C 20 F 42 in perfluorohexane so that L16828 (n-C 20 F 42 : melting point 167 ° C.) manufactured by Alfa Aesar was 0.03% by mass.
  • L16828 n-C 20 F 42 : melting point 167 ° C.
  • the dispersion liquid was sprayed onto a polypropylene nonwoven fabric using a Ruskin nozzle, particles adhered to the polypropylene nonwoven fabric in a solid content of 0.13 g / m 2 .
  • the mode particle diameter after solvent evaporation was measured by the DMA-CNC method, it was 18 nm.
  • the polypropylene nonwoven fabric to which the particles were attached was electretized by a corona discharge method to produce an electret filter. The evaluation results of the obtained electret filter are shown in Table 1.
  • Example 3 An aqueous dispersion of polytetrafluoroethylene (melting point: 330 ° C.) was heated to 300 ° C. and the surfactant component was removed and dispersed in perfluorohexane to a concentration of 1% by mass (solubility is 0.1). After that, the dispersion was sprayed onto a polypropylene nonwoven fabric using a Ruskin nozzle. As a result, 0.96 g / m 2 of particles were adhered in solid content. When the mode particle diameter after solvent evaporation was measured by the DMA-CNC method, it was 210 nm. Finally, the polypropylene nonwoven fabric to which the particles were attached was electretized by a corona discharge method to produce an electret filter. The evaluation results of the obtained electret filter are shown in Table 1.
  • Example 4 By suspension polymerization, a random copolymer (glass transition temperature (Tg): 61 ° C.) in which the mass ratio of dicyclopentanyl methacrylate to 2- (perfluorohexyl) ethyl methacrylate was 1: 9 was obtained.
  • the random copolymer was pulverized in perfluorohexane, allowed to penetrate into the polypropylene nonwoven fabric as a dispersion, and the non-dissolved portion of the random copolymer particles dispersed in advance was adhered to the nonwoven fabric, followed by air drying. .
  • the adhesion amount of the random copolymer was 1.19 g / m 2 in terms of solid content, and the mode particle diameter was measured using a scanning electron microscope to be 260 nm.
  • the polypropylene nonwoven fabric to which the particles were attached was electretized by a corona discharge method to produce an electret filter. The evaluation results of the obtained electret filter are shown in Table 1.
  • Example 5 A random copolymer (Tg: 81 ° C.) having a mass ratio of dicyclopentanyl methacrylate to 2- (perfluorohexyl) ethyl methacrylate of 3: 7 was obtained by suspension polymerization. The random copolymer was pulverized in perfluorohexane, allowed to penetrate into the polypropylene nonwoven fabric as a dispersion, and the non-dissolved portion of the random copolymer particles dispersed in advance was adhered to the nonwoven fabric, followed by air drying. .
  • the adhesion amount of the random copolymer was 1.08 g / m 2 in terms of solid content, and the mode particle size was measured using a scanning electron microscope and found to be 240 nm.
  • the polypropylene nonwoven fabric to which the particles were attached was electretized by a corona discharge method to produce an electret filter. The evaluation results of the obtained electret filter are shown in Table 1.
  • SNOWTEX registered trademark
  • 1H, 2H, 2H-perfluorooctyltrimethoxysilane was diluted with isopropyl alcohol, the diluted solution was infiltrated into a polypropylene nonwoven fabric.
  • Electret filter can be obtained.
  • the filter of the present invention can be suitably used as, for example, a dust mask, various air conditioning elements, an air purifier, a cabin filter, and a filter for the purpose of protecting various devices.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Filtering Materials (AREA)
  • Electrostatic Separation (AREA)

Abstract

L'invention fourni un procédé de fabrication de filtre électret permettant une fabrication à bas coût et selon une technique simple, y compris sans mise en œuvre d'un composé perfluoro à chaîne longue. Plus précisément, l'invention concerne un procédé de fabrication de filtre électret tel que des particules à teneur en fluor ne comprenant sensiblement pas de métal ni de composé métallique, sont mises en adhésion sur un support. Le procédé de l'invention est caractéristique en ce que lesdites particules à teneur en fluor sont constituées d'un polymère à teneur en fluor obtenu à partir d'un composant monomère qui contient soit un composé polycyclique à teneur en fluor, soit un (méth) acrylate possédant une oléfine à teneur en fluor ou une chaîne latérale à teneur en fluor. En outre, le procédé de l'invention comporte une étape au cours de laquelle ledit polymère à teneur en fluor et ledit composé polycyclique à teneur en fluor mettent lesdites particules à teneur en fluor en adhésion sur le support, sans production de télomère de fluor de 8 atomes de carbone ou plus et dont tout l'hydrogène est substitué par un carbone, sous l'effet d'une hydrolyse, avec un point de fusion ou une température de transition vitreuse desdites particules à teneur en fluor supérieurs à 40°C, et à l'aide d'une phase liquide ou gazeuse dans laquelle lesdites particules à teneur en fluor sont dispersées.
PCT/JP2015/083522 2014-12-03 2015-11-30 Procédé de fabrication de filtre électret WO2016088692A1 (fr)

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JP2018103109A (ja) * 2016-12-27 2018-07-05 東洋紡株式会社 エレクトレットフィルターおよびエレクトレットフィルターの製造方法
JP2018103108A (ja) * 2016-12-27 2018-07-05 東洋紡株式会社 エレクトレットフィルター
CN111376487A (zh) * 2020-05-29 2020-07-07 山东华滋自动化技术股份有限公司 一种口罩打片机
KR102311742B1 (ko) * 2021-07-28 2021-10-12 강인종 방수 기능을 갖는 마스크 원단 제조 방법, 이에 의해 제조된 마스크 원단 및 마스크
WO2022091060A1 (fr) 2020-11-02 2022-05-05 3M Innovative Properties Company Fibres âme-gaine, bande fibreuse non tissée, et articles filtrants comprenant celles-ci
CN114945418A (zh) * 2020-01-23 2022-08-26 东丽株式会社 驻极体熔喷无纺布、使用其而成的过滤器滤材及空气过滤器、以及驻极体熔喷无纺布的制造方法
CN115538181A (zh) * 2022-11-04 2022-12-30 广东省美净滤清器有限公司 一种除尘用高效耐衰退驻极体滤材及其制备方法
WO2024161928A1 (fr) * 2023-02-03 2024-08-08 東レ株式会社 Particule de polymère contenant du fluor

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JP2018103109A (ja) * 2016-12-27 2018-07-05 東洋紡株式会社 エレクトレットフィルターおよびエレクトレットフィルターの製造方法
JP2018103108A (ja) * 2016-12-27 2018-07-05 東洋紡株式会社 エレクトレットフィルター
CN114945418A (zh) * 2020-01-23 2022-08-26 东丽株式会社 驻极体熔喷无纺布、使用其而成的过滤器滤材及空气过滤器、以及驻极体熔喷无纺布的制造方法
CN114945418B (zh) * 2020-01-23 2024-06-04 东丽株式会社 驻极体熔喷无纺布、滤材及空气过滤器
CN111376487A (zh) * 2020-05-29 2020-07-07 山东华滋自动化技术股份有限公司 一种口罩打片机
CN111376487B (zh) * 2020-05-29 2020-08-25 山东华滋自动化技术股份有限公司 一种口罩打片机
WO2022091060A1 (fr) 2020-11-02 2022-05-05 3M Innovative Properties Company Fibres âme-gaine, bande fibreuse non tissée, et articles filtrants comprenant celles-ci
KR102311742B1 (ko) * 2021-07-28 2021-10-12 강인종 방수 기능을 갖는 마스크 원단 제조 방법, 이에 의해 제조된 마스크 원단 및 마스크
CN115538181A (zh) * 2022-11-04 2022-12-30 广东省美净滤清器有限公司 一种除尘用高效耐衰退驻极体滤材及其制备方法
WO2024161928A1 (fr) * 2023-02-03 2024-08-08 東レ株式会社 Particule de polymère contenant du fluor

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