WO2021033700A1 - エレクトレット及びそれを用いたフィルター - Google Patents
エレクトレット及びそれを用いたフィルター Download PDFInfo
- Publication number
- WO2021033700A1 WO2021033700A1 PCT/JP2020/031197 JP2020031197W WO2021033700A1 WO 2021033700 A1 WO2021033700 A1 WO 2021033700A1 JP 2020031197 W JP2020031197 W JP 2020031197W WO 2021033700 A1 WO2021033700 A1 WO 2021033700A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electret
- magnesium
- mmaq
- polyolefin resin
- filter
- Prior art date
Links
- 239000002245 particle Substances 0.000 claims abstract description 40
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 31
- 239000011777 magnesium Substances 0.000 claims abstract description 31
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 31
- 238000009423 ventilation Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 52
- 239000000835 fiber Substances 0.000 claims description 50
- -1 nitrogen-containing compound Chemical class 0.000 claims description 44
- 238000002834 transmittance Methods 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000035515 penetration Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 17
- 239000002657 fibrous material Substances 0.000 description 13
- 239000004745 nonwoven fabric Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 159000000003 magnesium salts Chemical class 0.000 description 8
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002681 magnesium compounds Chemical class 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 125000005313 fatty acid group Chemical group 0.000 description 4
- 235000019359 magnesium stearate Nutrition 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000004378 air conditioning Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001523 electrospinning Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical group CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000011045 prefiltration Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- DOTYDHBOKPPXRB-UHFFFAOYSA-N 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioic acid Chemical compound CCCCC(C(O)=O)(C(O)=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DOTYDHBOKPPXRB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 208000016253 exhaustion Diseases 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004665 fatty acids Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000005596 ionic collisions Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229940105112 magnesium myristate Drugs 0.000 description 1
- 229940063002 magnesium palmitate Drugs 0.000 description 1
- 229940057948 magnesium stearate Drugs 0.000 description 1
- OBQVOBQZMOXRAL-UHFFFAOYSA-L magnesium;docosanoate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O OBQVOBQZMOXRAL-UHFFFAOYSA-L 0.000 description 1
- BJZBHTNKDCBDNQ-UHFFFAOYSA-L magnesium;dodecanoate Chemical compound [Mg+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BJZBHTNKDCBDNQ-UHFFFAOYSA-L 0.000 description 1
- ABSWXCXMXIZDSN-UHFFFAOYSA-L magnesium;hexadecanoate Chemical compound [Mg+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O ABSWXCXMXIZDSN-UHFFFAOYSA-L 0.000 description 1
- DMRBHZWQMKSQGR-UHFFFAOYSA-L magnesium;tetradecanoate Chemical compound [Mg+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O DMRBHZWQMKSQGR-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- AXLHVTKGDPVANO-UHFFFAOYSA-N methyl 2-amino-3-[(2-methylpropan-2-yl)oxycarbonylamino]propanoate Chemical compound COC(=O)C(N)CNC(=O)OC(C)(C)C AXLHVTKGDPVANO-UHFFFAOYSA-N 0.000 description 1
- FDAKZQLBIFPGSV-UHFFFAOYSA-N n-butyl-2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CCCCNC1CC(C)(C)NC(C)(C)C1 FDAKZQLBIFPGSV-UHFFFAOYSA-N 0.000 description 1
- HRYSOBDFNHXNTM-UHFFFAOYSA-N n-butylbutan-1-amine;1,3,5-triazine Chemical compound C1=NC=NC=N1.CCCCNCCCC HRYSOBDFNHXNTM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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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
- B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
- B01D39/083—Filter cloth, i.e. woven, knitted or interlaced material of organic material
-
- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
- B01D39/1615—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of natural origin
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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
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
- B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
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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
- B01D39/1692—Other shaped material, e.g. perforated or porous sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0001—Making filtering elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
- B01D2239/0216—Bicomponent or multicomponent fibres
- B01D2239/0225—Side-by-side
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
- B01D2239/0216—Bicomponent or multicomponent fibres
- B01D2239/0233—Island-in-sea
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0435—Electret
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0622—Melt-blown
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0627—Spun-bonded
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0631—Electro-spun
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/12—Special parameters characterising the filtering material
- B01D2239/1233—Fibre diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
- B01D46/0032—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions using electrostatic forces to remove particles, e.g. electret filters
Definitions
- the present invention relates to an electret and a filter using the electret.
- porous filters for dust collection, protection, ventilation, etc. have been used in dust masks, various air conditioning elements, air purifiers, cabin filters, and various devices.
- filters made of fibrous material have high porosity, long life, and low air resistance, so they are widely used.
- particles are captured on the fiber by a mechanical collection mechanism such as contact adhesion, diffusion, and inertial collision. These mechanisms vary depending on the physical characteristics of the particles, the fiber diameter of the filter, the passing wind speed of the particles, etc., but in a practical usage environment, when the aerodynamic equivalent diameter of the captured particles is about 0.1 to 1.0 ⁇ m. It is known that the particle collection efficiency of the filter is the lowest.
- a method of using an electrical attractive force together is known.
- a method of charging a particle to be collected a method of charging a filter, a method of installing a filter in an electric field, and the like are known, and a method of combining a plurality of the above methods is also known.
- a method of applying an electric charge to the filter a method of arranging a filter between the electrodes and dielectrically polarization the filter during ventilation and a method of applying an electrostatic charge having a long life to the insulating material are known, and particularly in the case of the latter method. Filters containing such an insulating material are widely used as electret filters because they do not require energy such as an external power source.
- an electrostatic charge to the fibrous material by a method of contacting or colliding the liquid with the fibrous material (liquid contact charging method) to obtain an electret.
- a fibrous material formed from a mixture of a resin containing a polyolefin resin as a main component and a nitrogen-containing compound such as a hindered amine compound is brought into contact with a liquid such as water.
- Electrets to which electrostatic charges are applied are known.
- Patent Documents 1 to 3 are disclosed as an electret web in which a fibrous material containing a polyolefin resin as a main component is charged by a liquid contact charging method.
- Patent Document 1 discloses a non-woven electlet web containing a fiber produced from a thermoplastic polymer material, and the thermoplastic polymer material is produced into the fiber by treatment with a polymer and a polar liquid.
- a first additive a carboxylic acid having 29-50 carbon atoms and one or two primary and / or secondary amino groups.
- Patent Document 2 discloses an electret material in which a reinforcing material is laminated on a carrier to which an electrostatic charge is applied and which carries fluorine. Further, Patent Document 3 discloses an electret web containing a thermoplastic resin and a predetermined charge strengthening additive.
- the present invention includes the following inventions.
- the electret of the present invention and the filter using the electret have an excellent QF value.
- the electlet of the present invention contains a polyolefin resin and a nitrogen-containing compound, and the nitrogen-containing compound is contained in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin, and the content ratio of the magnesium element in the electlet is high. It is 5 to 100 ppm, and the QF value of the electlet is 1.00 mmAq -1 or more.
- the electret of the present invention uses a polyolefin resin having high hydrophobicity and high electrical resistance from the viewpoint of the degree of freedom in shape and the charge stability of the electret.
- the polyolefin resin include homopolymers of olefins such as ethylene, propylene, butylene, hexene, octene, butadiene, isoprene, chloroprene, methyl-1-pentene, and cyclic olefins, and copolymers composed of two or more of the above olefins. Can be mentioned.
- the polyolefin resin As the polyolefin resin, one of the above-mentioned polymers or copolymers may be selected and used alone, or two or more kinds may be selected and used in combination.
- the polyolefin resin preferably contains at least one selected from polypropylene and polymethylpentene, and more preferably polypropylene.
- the content ratio of the polyolefin resin in 100 parts by mass of the electret is preferably 80 parts by mass or more, more preferably 85 parts by mass or more, further preferably 90 parts by mass or more, and 95 parts by mass or more. It is particularly preferable, and most preferably 97 parts by mass or more.
- the upper limit of the content ratio of the polyolefin resin is not particularly limited, and is, for example, 99.5 parts by mass or less, preferably 99 parts by mass or less.
- the resin contained on the left and right sides of the fiber such as the sea score fiber and the side-by-side fiber and the core sheath is changed, only the portion containing the polyolefin resin is used as the electret of the present invention.
- the content ratio of the nitrogen-containing compound to 100 parts by mass of the polyolefin resin is 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, and 0.75 to 1.5 parts by mass. More preferred.
- two or more kinds of fibers are mixed in the electret, or when two or more kinds of resins are mixed in one fiber, it means the ratio of the nitrogen-containing compound contained in the polyolefin resin.
- the polyolefin resin can be discriminated.
- the content ratio of the nitrogen-containing compound is lower than 0.1 parts by mass, the charge amount becomes low and the filtration characteristics deteriorate, and when the content ratio is higher than 5 parts by mass, the hygroscopicity increases and the stability as an electret becomes stable. Lost.
- the content ratio of the nitrogen-containing compound in 100 parts by mass of the electret is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and 0.75 to 1.5 parts by mass. It is more preferable to have.
- the nitrogen-containing compound is not particularly limited as long as it can obtain the above-mentioned desired properties, but is preferably a hindered amine compound containing at least one of a 2,2,6,6-tetramethylpiperidyl structure and a triazine structure. It is more preferable that the hindered amine compound contains a 2,2,6,6-tetramethylpiperidine structure and a triazine structure.
- the hindered amine compound is not particularly limited, but for example, poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidil) imino ⁇ ] (Kimasorb® 944LD, BASF Dimethyl-1- (2 hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethyl-4-piperidin polycondensate (Chinubin® 622LD, manufactured by BASF Japan) ), 2-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -2-butylpropanediate bis [1,2,2,6,6-pentamethyl-4- Piperidinyl] (Tinubin® 144, manufactured by BASF Japan, Inc.), Dibutyl
- a 2,2,6,6-tetramethylpiperidine structure and a triazine structure it is preferable to include a 2,2,6,6-tetramethylpiperidine structure and a triazine structure, and more preferably Kimasorb (registered trademark) 944LD or Kimasorb (registered trademark) 2020FD.
- the hindered amine compound one of the above compounds may be used alone, or two or more of them may be used in combination.
- the content ratio of the magnesium element in the electret is 5 ppm or more and 100 ppm or less, preferably 10 ppm or more and 70 ppm or less, more preferably 15 ppm or more and less than 40 ppm, and further preferably 15 ppm or more and 35 ppm or less.
- the magnesium element content is too low or too high, the amount of charge in the electret is small, so that the ventilation resistance is small and the filtration performance is insufficient.
- the content ratio of the magnesium element in 100 parts by mass of the polyolefin resin is preferably 5 ppm or more and 100 ppm or less, more preferably 10 ppm or more and 70 ppm or less, further preferably 15 ppm or more and less than 40 ppm, and particularly preferably 15 ppm or more and 35 ppm or less. Is.
- the content of the magnesium element is within the above range, an electret having a large ventilation resistance and high filtration performance can be obtained.
- the method of adding the magnesium element to the polyolefin resin is not particularly limited as long as the desired properties can be obtained, but the surface of the electlet is subjected to melt mixing, dissolution mixing, ion collision, transpiration adhesion, supercriticality, exhaustion treatment, or the like. It is preferable that at least a part of the magnesium element is present. Since the polyolefin resin is stable against an organic solvent or an aqueous acid-alkali solution, it is preferable to perform crushing mixing or dispersion mixing when mixing or the like, or to give the magnesium compound excellent melt-mixability. It is also a preferable method to add a magnesium compound in advance when polymerizing the polyolefin resin.
- magnesium compounds such as magnesium salts, ionomers, and various chelates can be used.
- fatty acid magnesium salts which are composites with organic substances. Is preferably dissolved in the molten polyolefin resin.
- the electlet of the present invention preferably contains a magnesium salt, and is selected from the group consisting of a fatty acid magnesium salt, an alicyclic magnesium salt, and an aromatic magnesium salt. It is more preferable that the amount is at least one, and it is more preferable that the magnesium salt is contained.
- the melting point of the magnesium salt is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and the thermal decomposition temperature is preferably 200 ° C. or higher. If the thermal decomposition temperature or melting point is low, the decomposition products may disperse or become sticky during processing or use.
- the upper limit of the thermal decomposition temperature or melting point of the magnesium salt is not particularly limited, but is, for example, 300 ° C. or lower.
- the fatty acid magnesium salt is not particularly limited, but those having a fatty acid group having 10 to 50 carbon atoms are preferable, those having a fatty acid group having 12 to 30 carbon atoms are more preferable, and those having a fatty acid group having 16 to 22 carbon atoms are preferable. Is even more preferable.
- the fatty acid magnesium salt preferably has a linear fatty acid group, and may have one or two fatty acid chains that bind to magnesium, but it is preferably two.
- Specific examples of the fatty acid magnesium salt include magnesium salts of linear saturated fatty acids such as magnesium laurate, magnesium myristate, magnesium palmitate, magnesium stearate, and magnesium behenate; magnesium oleate, magnesium ersinate, and the like.
- Magnesium salts of linear unsaturated fatty acids are mentioned, but from the viewpoint of melting point and reactivity, magnesium salts of linear saturated fatty acids are preferable, and magnesium stearate is more preferable.
- the above-mentioned characteristics can be expressed by one component by using a component in which a magnesium compound and a nitrogen-containing compound are integrated in advance.
- the method for preparing or producing the magnesium compound is not particularly limited, and a commercially available magnesium compound may be used, or a magnesium compound may be produced using magnesium before integration, and the chelating compound and magnesium are used. It may be added separately and reacted by a method such as melting before the electlet processing.
- Metal elements other than magnesium element are preferably contained in a very small amount or not present at all because they hinder the stability and charge stability of the polyolefin resin as a polymer and charge generation.
- the content of the metal element other than the magnesium element in the electret is preferably 500 ppm or less, more preferably 250 ppm or less, still more preferably 100 ppm or less, and most preferably 50 ppm or less for each metal element.
- the alkali metal and the colored transition metal element are not contained, and specifically, the total content of the alkali metal and the colored transition metal element in the electlet is preferably 100 ppm or less, more preferably 50 ppm or less. It is more preferably 25 ppm or less, and most preferably 10 ppm or less.
- Electret QF value of the present invention is 1.00MmAq -1 or more, preferably 1.20MmAq -1 or more, and more preferably 1.45MmAq -1 or more.
- the upper limit of the QF value is not particularly limited, but is, for example, 6.00 mmAq -1 or less, preferably 4.00 mmAq -1 or less, and more preferably 2.00 mmAq -1 or less. If the QF value is less than 1.00 mmAq -1 , the particles are not sufficiently captured by the electret and the filtration performance is insufficient.
- the QF value is a value calculated by the following formula, and the method for measuring the particle transmittance and the ventilation resistance will be described later.
- the “particle transmittance” refers to the particle transmittance when particles having a particle size of 0.3 to 0.5 ⁇ m are targeted for collection.
- QF [mmAq -1 ] -[ln (particle transmittance (%) / 100)] / [ventilation resistance (mmAq)]
- the particle transmittance in the electret of the present invention is preferably 15% or less, more preferably 5% or less, further preferably 2% or less, and particularly preferably 0.5% or less.
- the lower limit of the particle transmittance is not particularly limited, but is 0.00001% or more in consideration of the balance with the air permeability.
- the ventilation resistance of the electret of the present invention is preferably 1.0 mmAq or more, more preferably 2.0 mmAq or more, and further preferably 3.0 mmAq or more.
- the upper limit of the ventilation resistance is not particularly limited, but is 10 mmAq or less, preferably 8.0 mmAq or less.
- the fineness of the electret of the present invention is preferably 0.5 to 15 ⁇ m, more preferably 0.7 to 10 ⁇ m, still more preferably 0.9 to 7 ⁇ m, and most preferably 1.0 to 3.5 ⁇ m.
- the fineness is calculated by using a scanning electron microscope, measuring the diameters of 50 fibers in the same field of view so that the fibers do not overlap, and calculating the geometric mean. If the fibers are too thin, clogging and thread breakage are likely to occur, and if the fibers are too thick, the thickness becomes large, which makes it difficult to improve efficiency and form a pleated shape.
- the shape of the electret of the present invention is not particularly limited, and may be any shape such as a fibrous material, an injection molded product, a film shape, a powdered material, or a particulate matter, but for the purpose of gas purification or the like. When used as a filter, it is preferably a fibrous material. As the electret of the present invention, one molded into an appropriate shape and thickness according to the intended use can be used.
- the fibrous material is preferably a fiber aggregate
- the fiber aggregate is, for example, a fibrous material obtained from a woven or knitted fabric made of long fibers or short fibers, a non-woven fabric, a cotton-like material, or a stretched film. Things can be mentioned.
- the fiber aggregate is recognized to have a fibrous form when the surface of the electlet is observed with a device such as a scanning electron microscope or an optical microscope, and at least a part of the fibers constituting the fiber aggregate is formed. It refers to the state of fusion and integration.
- the fiber aggregate is a non-woven fabric.
- a method for obtaining a non-woven fabric a method of sheeting short fibers such as single component fibers, composite fibers such as core sheath fibers and side-by-side fibers, and split fibers by carding, airlaid, wet papermaking method, etc., and a spunbond method consisting of continuous fibers.
- a conventionally known method such as a method obtained by a melt-blown method, an electrospinning method, a force spinning method, or the like can be used.
- non-woven fabrics obtained by the melt blown method, electrospinning method, or force spinning method which can easily obtain fineness and fineness from the viewpoint of effectively utilizing the mechanical collection mechanism, are preferable and do not require treatment of residual solvent.
- the non-woven fabric obtained by the melt-blown method, the molten electrospinning method, or the molten force spinning method is more preferable, and the non-woven fabric obtained by the melt-blown method is particularly preferable.
- the average fiber diameter of the fibers used in the fibrous material is preferably 0.001 to 100 ⁇ m, more preferably 0.1 to 20 ⁇ m, further preferably 0.2 to 10 ⁇ m, and 0. It is particularly preferably .5 to 5 ⁇ m, and most preferably 1 to 3 ⁇ m.
- the average fiber diameter of the fiber is thicker than 100 ⁇ m, it is difficult to obtain a practical collection efficiency, and the efficiency is greatly reduced at the time of charge attenuation.
- the average fiber diameter of the fibers is smaller than 0.001 ⁇ m, it is difficult to produce a charged electret.
- the fibrous material may be a uniform product made of a single manufacturing method or material, or may be a mixture made of two or more materials having different manufacturing methods, materials and fiber diameters.
- the electret-forming method in the present invention is not particularly limited as long as it can obtain desired characteristics when the electret is used, but a method of contacting or colliding a liquid with the fibrous material (liquid contact charging method) is preferable, and liquid contact charging is preferable.
- An electret with high filtration characteristics can be obtained by the method. More specifically, a method of contacting or colliding the liquid with the fiber assembly by a method such as suction, pressurization, or ejection is preferable.
- the liquid to be contacted or collided is not particularly limited as long as it can obtain desired characteristics, but water is preferable from the viewpoint of handleability and performance.
- the conductivity and pH of water vary depending on the content of calcium ions and magnesium ions.
- a liquid in which a sub-component (component other than water) is added to water may be used, and the conductivity and pH of the liquid can be adjusted by the type and amount of the sub-component to be added.
- the liquid to be contacted or collided in the liquid contact charging method preferably has a pH of 1 to 11, more preferably 3 to 9, and even more preferably 5 to 7. Further, the liquid to be contacted or collided in the liquid contact charging method preferably has a conductivity of 100 ⁇ S / cm or less, more preferably 10 ⁇ S / cm or less, and further preferably 3 ⁇ S / cm or less.
- the electret of the present invention can be used in combination with other constituent members, if necessary. That is, the electret of the present invention can be used in combination with a pre-filter layer, a fiber protective layer, a reinforcing member, a functional fiber layer and the like.
- Examples of the pre-filter layer and fiber protective layer include spunbonded non-woven fabric, thermal-bonded non-woven fabric, and urethane foam, and examples of the reinforcing member include thermal-bonded non-woven fabric and various nets. Further, examples of the functional fiber layer include antibacterial and antiviral and colored fiber layers for the purpose of identification and design.
- the electret of the present invention and the filter using the same can be widely used due to the functions of dust collection, protection, ventilation, antifouling, waterproofing, etc. obtained by the present invention, and in particular, a dust mask, various air conditioning elements, and the like. It can be suitably used as an air purifier, a cabin filter, and a filter for the purpose of protecting various devices.
- Ventilation resistance A sample punched to 72 mm ⁇ is attached to an adapter with an effective ventilation diameter of 50 mm ⁇ , and a pipe with an inner diameter of 50 mm connected to a micro differential pressure gauge is connected up and down to ventilate at 10 cm / s and ventilate without a throttle. The resistance (pressure loss) was measured.
- Particle transmittance A sample punched to 72 mm ⁇ is attached to an adapter with an effective ventilation diameter of 50 mm ⁇ , and the particle transmittance of the filter is measured by the following method using a light scattering type particle counting device KC-01E manufactured by Rion. did. Evaluation particles: Atmospheric dust Wind speed: 10 cm / s Efficiency calculation: The number of particles having a particle size of 0.3 to 0.5 ⁇ m was measured by a light scattering counting method.
- Particle transmittance (%) (Number of particles with a particle size of 0.3 to 0.5 ⁇ m that has passed through the electlet ⁇ Number of particles with a particle size of 0.3 to 0.5 ⁇ m before permeation of the electlet)
- Example 1 Melt flow rate (MFR) 1200 g / 10 minutes, magnesium stearate (melting point: 88 ° C.) 0.00025 parts by mass in 100 parts by mass of polypropylene homopolymer with magnesium concentration of 0.1 ppm or less, Kimasorb manufactured by BASF, which is a hindered amine compound
- MFR Melt flow rate 1200 g / 10 minutes
- magnesium stearate melting point: 88 ° C.
- Kimasorb manufactured by BASF which is a hindered amine compound
- a fiber sheet having a grain size of 20 g / m 2 was obtained by spinning 1 part by mass of (registered trademark) 944 at a resin temperature of 260 ° C. and an air temperature of 260 ° C. using a melt blown apparatus.
- the obtained fiber sheet was charged by colliding with water having an electrical conductivity of 0.7 ⁇ S / cm and a pH of 6.8, and then left at 100 ° C. for 30 minutes to dry to obtain an electret filter. It was.
- the ventilation resistance was 3.60 mmAq
- the QF value was 1.13 mmAq -1
- the magnesium concentration was 7.8 ppm.
- Examples 2 to 8 Comparative Examples 1 to 4> An electret filter was prepared in the same manner as in Example 1 except that the amount of magnesium stearate to be added was the amount shown in Table 1.
- the content ratios of the magnesium element and the nitrogen-containing compound were within the predetermined range, and the electret filter charged by colliding with water showed a large QF value and high filtration characteristics.
- the electrets of Examples 1 to 8 using a scanning electron microscope, 50 fiber diameters were measured in the same field of view so that the fibers did not overlap, and the fineness was calculated by the geometric mean. The fineness of was also in the range of 2 to 2.5 ⁇ m.
- the electret of the present invention has excellent filtration performance, it can be used as a filter in various applications such as dust masks and air purifiers.
Abstract
Description
すなわち、本発明は、以下の発明を含む。
[1]ポリオレフィン樹脂及び含窒素化合物を含むエレクトレットであって、前記ポリオレフィン樹脂100質量部に対し、前記含窒素化合物が0.1~5質量部含まれており、前記エレクトレットにおけるマグネシウム元素の含有割合が5~100ppmであり、粒径0.3~0.5μmの粒子を捕集対象としたとき、下記式で表わされるQF値が1.00mmAq-1以上であることを特徴とするエレクトレット。
QF[mmAq-1]=-[ln(粒子透過率(%)/100)]/[通気抵抗(mmAq)]
[2]脂肪酸マグネシウム塩を含む上記[1]に記載のエレクトレット。
[3]前記含窒素化合物がヒンダードアミン系化合物を含む上記[1]又は[2]に記載のエレクトレット。
[4]繊維集合体である上記[1]~[3]のいずれかに記載のエレクトレット。
[5]メルトブローン法により作製された上記[1]~[4]のいずれかに記載のエレクトレット。
[6]上記[1]~[5]のいずれかに記載のエレクトレットを用いたフィルター。
本発明のエレクトレットは、形状の自由度及びエレクトレットの電荷安定性の観点から、疎水性かつ電気抵抗の高いポリオレフィン樹脂を用いている。ポリオレフィン樹脂としては、例えば、エチレン、プロピレン、ブチレン、ヘキセン、オクテン、ブタジエン、イソプレン、クロロプレン、メチル-1-ペンテン、環状オレフィンなどのオレフィンの単独重合体や2種類以上の上記オレフィンからなる共重合体が挙げられる。ポリオレフィン樹脂は上記重合体又は共重合体の1種を選択して単独で使用してもよいし、2種以上を選択して組み合わせて使用してもよい。ポリオレフィン樹脂は、ポリプロピレン及びポリメチルペンテンから選ばれる少なくとも1種を含むことが好ましく、ポリプロピレンを含むことがより好ましい。エレクトレット100質量部中におけるポリオレフィン樹脂の含有割合が80質量部以上であることが好ましく、85質量部以上であることがより好ましく、90質量部以上であることがさらに好ましく、95質量部以上であることが特に好ましく、97質量部以上であることが最も好ましい。ポリオレフィン樹脂の含有割合の上限は特に限定されず、例えば99.5質量部以下であり、99質量部以下であることが好ましい。なお、シースコア繊維やサイドバイサイド繊維など繊維の左右や芯鞘で含有している樹脂を変えている場合には、ポリオレフィン樹脂が含まれている部分のみを本発明のエレクトレットとする。
ポリオレフィン樹脂100質量部中に対する含窒素化合物の含有割合が0.1~5質量部であり、0.5~3質量部であることが好ましく、0.75~1.5質量部であることがより好ましい。なお、エレクトレットにおいて2種類以上の繊維を混ぜている場合や一つの繊維に2種類以上の樹脂を混ぜている場合にはポリオレフィン樹脂に含まれている含窒素化合物の割合のことを指す。エレクトレット中にポリオレフィン以外の樹脂が含まれている場合であっても、ポリオレフィン以外の樹脂は溶媒・酸塩基に溶解したり、染色性が異なるため、判別可能であり、DSCやNMRなどの定量法でもポリオレフィン樹脂を判別可能である。含窒素化合物の含有割合が0.1質量部より低い場合には電荷量が低くなるため濾過特性が低下してしまい、5質量部より高い場合には吸湿性の増大によりエレクトレットとしての安定性が失われる。
エレクトレットにおけるマグネシウム元素の含有割合が5ppm以上100ppm以下であり、好ましくは10ppm以上70ppm以下であり、より好ましくは15ppm以上40ppm未満であり、さらに好ましくは15ppm以上35ppm以下である。マグネシウム元素の含有率が低すぎる場合も高すぎる場合も、エレクトレットにおける電荷量が小さいため、通気抵抗が小さく、濾過性能も不十分である。
本発明のエレクトレットのQF値は、1.00mmAq-1以上であり、1.20mmAq-1以上であることが好ましく、1.45mmAq-1以上であることがより好ましい。QF値の上限は特に限定されないが、例えば6.00mmAq-1以下であり、好ましくは4.00mmAq-1以下であり、より好ましくは2.00mmAq-1以下である。QF値が1.00mmAq-1を下回るとエレクトレットによって粒子が十分に捕捉されておらず、濾過性能が不十分である。なお、QF値は下記の式により算出される値であり、粒子透過率及び通気抵抗の測定方法については後述する。また、本明細書では「粒子透過率」は、粒径0.3~0.5μmの粒子を捕集対象としたときの粒子透過率のことを指す。
QF[mmAq-1]=-[ln(粒子透過率(%)/100)]/[通気抵抗(mmAq)]
本発明のエレクトレットの形状は特に限定されず、例えば、繊維状物、射出成型体、フィルム形状、粉末状物、粒子状物などのいずれの形状であってもよいが、気体浄化等の目的でフィルターとして用いる場合には繊維状物であることが好ましい。本発明のエレクトレットとしては、用途に応じて適当な形状および厚みに成形したものを使用することができる。
本発明におけるエレクトレット化法はエレクトレットの使用時に所望の特性が得られるものであれば特に制限されないが、上記繊維状物に液体を接触又は衝突させる方法(液体接触荷電法)が好ましく、液体接触荷電法により高い濾過特性を有するエレクトレットを得ることができる。より具体的には、繊維集合体に吸引、加圧、噴出などの方法により液体を接触又は衝突させる方法であることが好ましい。
本発明のエレクトレットは必要に応じて他の構成部材と併用して用いることができる。すなわち、本発明のエレクトレットはプレフィルター層、繊維保護層、補強部材、機能性繊維層などと組み合わせて用いることができる。
試料0.5gを白金製るつぼに秤量し、ホットプレート上で400℃まで予備炭化を行った。その後、ヤマト科学社製電気炉FO610型を用いて、550℃で8時間灰化処理を実施した。灰化後、6.0Nの塩酸を3mL添加し、ホットプレート上で100℃で酸分解を行い、塩酸が完全に揮発するまで加熱処理を行った。酸分解終了後に、1.2Nの塩酸を20mL添加し、これを測定検液として日立ハイテクサイエンス社製ICP発光分析装置 SPECTROBLUE型を用いて、目的元素の標準液で作成した検量線により、検液中のマグネシウム量の定量を実施し、試料中におけるマグネシウム濃度を下記式により求めた。
試料中のマグネシウム濃度:A(ppm(=mg/kg))
上記検液中のマグネシウム濃度:B(mg/L)
試料を用いない(試料を白金製るつぼに秤量しない)以外は上記と同様の方法で測定したマグネシウム濃度:C(mg/L)
A=(B-C)×(20÷1000)(L)/(0.5÷1000)(kg)
72mmφに打ち抜いたサンプルを有効通気径50mmφアダプターに装着し、微差圧計を接続した内径50mmの配管を上下に連結、10cm/sにて通風し、絞りの無い状態での通気抵抗(圧力損失)を計測した。
72mmφに打ち抜いたサンプルを有効通気径50mmφのアダプターに装着し、光散乱式粒子計数装置リオン社製KC-01Eを用いて以下の方法にて、フィルターの粒子透過率を実施した。
評価粒子:大気塵
風速 :10cm/s
効率算出:粒径0.3~0.5μmの粒子個数を光散乱計数法により測定した。
粒子透過率(%)=(エレクトレットを透過した粒径0.3~0.5μmの粒子個数÷エレクトレット透過前の粒径0.3~0.5μmの粒子個数)
上記(2)で測定した通気抵抗及び上記(3)で測定した粒子透過率の値を用いて、以下の式よりQF値を求めた。
QF[mmAq-1]=-[ln(粒子透過率(%)/100)]/[通気抵抗(mmAq)]
メルトフローレート(MFR)1200g/10分、マグネシウム濃度0.1ppm以下のポリプロピレンホモポリマー100質量部にステアリン酸マグネシウム(融点:88℃)を0.00025質量部、ヒンダードアミン系化合物であるBASF社製キマソーブ(登録商標)944を1質量部添加したものを、メルトブローン装置を用い、樹脂温度260℃、空気温度260℃にて紡糸し目付20g/m2の繊維シートを得た。得られた繊維シートに対して、電気伝導度0.7μS/cm、pH6.8の水を衝突させることで荷電を行った後に100℃にて30分放置することで乾燥を行いエレクトレットフィルターを得た。通気抵抗は3.60mmAq、QF値は1.13mmAq-1、マグネシウム濃度は7.8ppmであった。
添加するステアリン酸マグネシウムの量を表1に記載の量とした以外は実施例1と同様にエレクトレットフィルターを作製した。
ヒンダードアミン系化合物を添加しなかった以外は実施例5と同様にエレクトレットフィルターを作製した。
得られた繊維シートに対してコロナ放電法により荷電を行った以外は実施例5と同様にエレクトレットフィルターを作製した。
Claims (6)
- ポリオレフィン樹脂及び含窒素化合物を含むエレクトレットであって、
前記ポリオレフィン樹脂100質量部に対し、前記含窒素化合物が0.1~5質量部含まれており、
前記エレクトレットにおけるマグネシウム元素の含有割合が5~100ppmであり、
粒径0.3~0.5μmの粒子を捕集対象としたとき、下記式で表わされるQF値が1.00mmAq-1以上であることを特徴とするエレクトレット。
QF[mmAq-1]=-[ln(粒子透過率(%)/100)]/[通気抵抗(mmAq)] - 脂肪酸マグネシウム塩を含む請求項1に記載のエレクトレット。
- 前記含窒素化合物がヒンダードアミン系化合物を含む請求項1又は2に記載のエレクトレット。
- 繊維集合体である請求項1~3のいずれかに記載のエレクトレット。
- メルトブローン法により作製された請求項1~4のいずれかに記載のエレクトレット。
- 請求項1~5のいずれかに記載のエレクトレットを用いたフィルター。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6346640B2 (ja) | 1977-12-07 | 1988-09-16 | Tucker Arthur Raymond | |
WO2003060216A1 (fr) * | 2002-01-11 | 2003-07-24 | Japan Vilene Company, Ltd. | Procédé et dispositif de production d'électret |
JP2013540904A (ja) * | 2010-08-23 | 2013-11-07 | ファイバーウェブ コロビン ゲーエムベーハー | エレクトレット特性を有する不織ウェブ及び繊維、その製造方法並びにその使用 |
JP2016520728A (ja) * | 2013-04-19 | 2016-07-14 | スリーエム イノベイティブ プロパティズ カンパニー | 帯電強化添加剤を含むエレクトレットウェブ |
JP2018040098A (ja) * | 2016-08-31 | 2018-03-15 | 東レ株式会社 | エレクトレット繊維シート、およびエアフィルター濾材 |
JP2018523761A (ja) * | 2015-07-07 | 2018-08-23 | スリーエム イノベイティブ プロパティズ カンパニー | 帯電強化添加剤を含むエレクトレットウェブ |
JP2018202369A (ja) | 2017-06-09 | 2018-12-27 | 東洋紡株式会社 | エレクトレット材料およびそれを用いたフィルター、並びにエレクトレットフィルターの製造方法 |
JP2019151213A (ja) | 2018-03-02 | 2019-09-12 | トヨタ自動車株式会社 | インストルメントパネル構造 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10235571A1 (de) * | 2002-08-03 | 2004-02-12 | Clariant Gmbh | Verwendung von Salzen schichtartiger Doppelhydroxide als Ladungssteuermittel |
US20060079145A1 (en) * | 2004-10-13 | 2006-04-13 | Hollingsworth & Vose Company | Filter media with charge stabilizing and enhancing additives |
JP5047848B2 (ja) * | 2008-03-14 | 2012-10-10 | クラレクラフレックス株式会社 | 生分解性不織布のエレクトレット体及びフィルター |
JP2014233687A (ja) * | 2013-06-04 | 2014-12-15 | 東洋紡株式会社 | エレクトレットフィルター |
JP2018095973A (ja) * | 2016-12-08 | 2018-06-21 | 東レ株式会社 | メルトブロー不織布 |
-
2020
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6346640B2 (ja) | 1977-12-07 | 1988-09-16 | Tucker Arthur Raymond | |
WO2003060216A1 (fr) * | 2002-01-11 | 2003-07-24 | Japan Vilene Company, Ltd. | Procédé et dispositif de production d'électret |
JP2013540904A (ja) * | 2010-08-23 | 2013-11-07 | ファイバーウェブ コロビン ゲーエムベーハー | エレクトレット特性を有する不織ウェブ及び繊維、その製造方法並びにその使用 |
JP2016520728A (ja) * | 2013-04-19 | 2016-07-14 | スリーエム イノベイティブ プロパティズ カンパニー | 帯電強化添加剤を含むエレクトレットウェブ |
JP2018523761A (ja) * | 2015-07-07 | 2018-08-23 | スリーエム イノベイティブ プロパティズ カンパニー | 帯電強化添加剤を含むエレクトレットウェブ |
JP2018040098A (ja) * | 2016-08-31 | 2018-03-15 | 東レ株式会社 | エレクトレット繊維シート、およびエアフィルター濾材 |
JP2018202369A (ja) | 2017-06-09 | 2018-12-27 | 東洋紡株式会社 | エレクトレット材料およびそれを用いたフィルター、並びにエレクトレットフィルターの製造方法 |
JP2019151213A (ja) | 2018-03-02 | 2019-09-12 | トヨタ自動車株式会社 | インストルメントパネル構造 |
Non-Patent Citations (1)
Title |
---|
See also references of EP4019111A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021256425A1 (ja) * | 2020-06-18 | 2021-12-23 | 東洋紡株式会社 | ポリメチルペンテンのメルトブロー不織布及びその製造方法 |
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