WO2020203508A1 - Gas adsorbent - Google Patents

Gas adsorbent Download PDF

Info

Publication number
WO2020203508A1
WO2020203508A1 PCT/JP2020/013174 JP2020013174W WO2020203508A1 WO 2020203508 A1 WO2020203508 A1 WO 2020203508A1 JP 2020013174 W JP2020013174 W JP 2020013174W WO 2020203508 A1 WO2020203508 A1 WO 2020203508A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas adsorbent
activated carbon
filter medium
gas
adsorbent
Prior art date
Application number
PCT/JP2020/013174
Other languages
French (fr)
Japanese (ja)
Inventor
直貴 山賀
康裕 浅田
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2020518099A priority Critical patent/JPWO2020203508A1/ja
Publication of WO2020203508A1 publication Critical patent/WO2020203508A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A61L9/014—Deodorant compositions containing sorbent material, e.g. activated carbon
    • 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
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon

Definitions

  • the present invention relates to a gas adsorbent.
  • An air purifier is used for the purpose of removing dust and odorous gas components in the home.
  • deodorizing performance for various gases such as volatile organic compounds (VOC) and formaldehyde generated in a living environment where the air purifier is used is required.
  • VOCs have been shown to have unfavorable effects on the human body, and it is stipulated by the laws and ministerial ordinances of each country to control the indoor environmental concentration of VOCs below a certain level.
  • the air purifier is expected to perform as a removal device for this VOC.
  • air purifiers are required to have high removal efficiency for formaldehyde, which has a risk of being released from building materials such as wallpaper, which is a cause of sick house syndrome, and to extend its life.
  • the high removal efficiency for formaldehyde means that the operating time of the air purifier required to reduce the gas concentration in the predetermined space is short.
  • Prolonging the life of the removal efficiency for formaldehyde means that the removal efficiency for formaldehyde is maintained even after adsorbing a predetermined amount of formaldehyde gas.
  • the removal efficiency for formaldehyde is the space purification capacity (CADR: Clean Air Delivery Rate), and the life of the removal efficiency for formaldehyde is the cumulative purification amount (CCM: Cumulate Clean Mass). It is shown.
  • a dust collection sheet and a reinforcing sheet made of an electret-processed non-woven fabric are mixed with activated carbon and an adsorbent that adsorbs with formaldehyde by chemical reactivity.
  • a device including a dust collecting and deodorizing filter medium having a structure sandwiched between them has been proposed (see, for example, Patent Document 1).
  • the adsorbent contains activated carbon, and the activated carbon is expected to adsorb and remove odorous components such as butane and toluene.
  • activated carbon has a large number of pores, and the efficiency of adsorption and removal of n-butane by activated carbon changes depending on what these pores are. Specifically, when the pore diameter of 0.65 nm or less calculated by the MP method of activated carbon is 0.1 cc / g or more, the adsorption removal of n-butane of the adsorbent containing this activated carbon It is known that the efficiency of the above is improved (see, for example, Patent Document 2).
  • Patent Document 2 discloses an adsorbent containing activated carbon having a pore diameter of 0.65 nm or less and a pore volume of 0.1 cc / g or more calculated by the MP method. Further, Patent Document 2 discloses that the above-mentioned adsorbent containing activated carbon has excellent efficiency in adsorbing and removing n-butane, which is a low molecular weight aliphatic hydrocarbon having a low melting point and no polarity. ing. However, on the other hand, Patent Document 2 does not disclose at all that the above-mentioned adsorbent suppresses the desorption of n-butane once adsorbed on the air filter from the air filter. Naturally, Patent Document 2 does not disclose at all that the above-mentioned adsorbent suppresses the desorption of aromatic hydrocarbons such as toluene once adsorbed on the air filter from the air filter.
  • the present invention is a gas adsorbent capable of suppressing desorption of odorous components such as toluene once adsorbed on the air filter from the air filter, that is, suppressing secondary odor.
  • the challenge is to provide.
  • the gas adsorbent of the present invention that solves the above problems is a gas adsorbent containing activated carbon.
  • the pore volume of the activated carbon having a pore diameter of 0.4 to 2 nm calculated by the MP method is in the range of 0.40 to 0.55 cc / g, and the pore volume is MP.
  • the ratio of the activated carbon to the pore volume of all pores calculated by the method and the BJH method is 75% or more.
  • the gas adsorbent of the present invention preferably has any one of the following characteristics (1) to (3). (1)
  • the content of the activated carbon is 20% by mass or more with respect to the total of the gas adsorbent.
  • the gas adsorbent sheet of the present invention contains the gas adsorbent of the present invention.
  • the gas adsorbent of the present invention is held in at least one of one or more layers formed by two or more layers of non-woven fabric.
  • the air filter of the present invention includes the filter medium of the present invention.
  • an adsorbent capable of suppressing desorption of odorous components such as toluene once adsorbed on the air filter from the air filter, that is, capable of suppressing secondary odor.
  • the present invention can suppress the above-mentioned problem, that is, the desorption of odorous components such as toluene once adsorbed on the air filter from the air filter, that is, the secondary odor can be suppressed.
  • the present invention will be described in detail.
  • “mass” is synonymous with "weight”.
  • the gas adsorbent of the present invention contains activated carbon.
  • the activated carbon contained in the gas adsorbent of the present invention has the following pore structure. That is, the pore structure of the above activated carbon is such that the pore volume of the pores having a pore diameter of 0.4 to 2 nm calculated by the MP method of the activated carbon is in the range of 0.40 to 0.55 cc / g. Yes, and the pore volume is calculated by the MP method and the BJH method, and the ratio of the activated carbon to the pore volume of all pores is 75% or more.
  • the pore volume formed by the pores of a specific size (pores having a pore diameter in the range of 0.4 to 2 nm) is in a specific range (0.40 to 0). .55 cc / g), that is, there are a specific number of pores of a specific size in the activated carbon, and the pore volume of the pores having a pore diameter of 0.4 to 2 nm is fine.
  • the ratio to the pore volume is 75% or more, that is, the ratio of the pore volume of the pores having a pore diameter of less than 0.4 nm and the pore volume of the pores having a pore diameter of more than 2 nm to the total pore volume.
  • the gas adsorbent having activated carbon is excellent in the performance of adsorbing and removing odorous components such as toluene, and further, once adsorbed, the odorous components such as toluene are desorbed from the gas adsorbent. Is suppressed.
  • the mechanism by which this effect can be obtained is presumed to be as follows. That is, among the pores existing in the activated carbon, the pores having a pore diameter of 0.4 to 2 nm are excellent in the performance of adsorbing and removing odorous components such as toluene, and further, toluene once adsorbed in these pores. Odor components such as these have the characteristic that they are difficult to desorb from the pores. On the other hand, pores having a pore diameter of less than 0.4 nm are inferior in adsorption and removal performance of odorous components such as toluene, especially odorous components having a large molecular weight, and pores having a pore diameter of more than 2 nm are adsorbed in the pores.
  • the performance of suppressing the desorption of odorous components such as toluene (hereinafter, may be referred to as the desorption suppressing performance) is inferior.
  • the pore volume of the pores having a pore diameter of 0.4 to 2 nm calculated by the MP method of the activated carbon is in the range of 0.40 to 0.55 cc / g, and the pore volume is the above.
  • the pore structure in which the ratio of the activated carbon to the pore volume of the total pores calculated by the MP method and the BJH method is 75% or more identifies pores having excellent adsorption removal performance and desorption suppression performance of odorous components.
  • the ratio of the amount of pores having excellent adsorption removal performance and desorption suppressing performance of odorous components to the amount of all pores present in activated carbon is more than a specific value, that is, of the odorous components. It can be said that the pore structure has a pore structure in which the total amount of pores inferior in adsorption removal performance or pores inferior in desorption suppressing performance is less than a specific value. As a result, it is presumed that the performance of adsorbing and removing the odorous component of the gas adsorbent having activated carbon and the performance of suppressing desorption are both excellent.
  • the MP (MICROPORE) method is an analysis method that can quantify the distribution of pores in activated carbon in the pore size.
  • a method for analyzing the pore diameter and the pore volume of the activated carbon there are an MP (MICROPORE) method, a BJH (Barrett-Joiner-Halenda) method, and the like.
  • the MP method was adopted for the analysis of micropores having a pore diameter of 0.4 to 2 nm in which capillary condensation does not occur.
  • the BJH method was adopted for the analysis of macropores having a pore diameter of 2 nm or more among the pores contained in the activated carbon.
  • the pore volume of the total pores of the activated carbon calculated by the MP method and the BJH method in the present invention is the value of the pore volume obtained by the MP method and the value of the pore volume obtained by the BJH method. Refers to the total value of.
  • Activated carbon having the above-mentioned pore structure can be arbitrarily selected from known materials such as coconut shell, coal pitch, and phenol resin as a raw material, and pores are formed by high-temperature treatment with steam or chemical treatment with hydrochloric acid or the like. Obtained by adjusting the activation conditions. Above all, it is more preferable to use coconut shell as a raw material and select an activation method using steam because activated carbon having micropores having a pore size in the range of 0.4 to 2 nm can be easily obtained.
  • the content of activated carbon in the gas adsorbent of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more with respect to the entire gas adsorbent. preferable.
  • the upper limit of the content of activated carbon in the gas adsorbent is not particularly limited and may be 100% by mass, but may be, for example, 90% by mass or less, or 50% by mass or less.
  • the gas adsorbent of the present invention concentrates and retains gas on the surface of the constituent material by the action of intermolecular attractive force generated by contact with a gas component in the air as a constituent material of the gas adsorbent.
  • a physical adsorbent that substantially lowers the spatial concentration of the gas component.
  • the physical adsorbent can be arbitrarily selected from a physical adsorbent made of a porous substance such as zeolite or sepiolite.
  • a porous substance such as activated carbon or zeolite is used as a support, and an acid component such as phosphoric acid or hydrochloric acid is impregnated to the support to obtain an alkali component gas adsorbent, or carbon dioxide is added to the support.
  • an acid component such as phosphoric acid or hydrochloric acid
  • alkali component gas adsorbent or carbon dioxide is added to the support.
  • acid component gas adsorbents obtained by impregnating alkaline components such as sodium hydrogen and potassium carbonate, and aldehyde gas adsorbents obtained by impregnating primary to tertiary amine compound components. can do.
  • the gas adsorbent of the present invention preferably contains a chemical adsorbent that adsorbs an aldehyde by a chemical reaction. Since the gas adsorbent of the present invention contains a chemical adsorbent that adsorbs aldehydes by a chemical reaction, the adsorption capacity of formaldehyde can be improved and desorption after gas adsorption is small, so that it can be used as an air purifier. When used, it is preferable because it can suppress a decrease in the space removal capacity (CADR) of formaldehyde.
  • ACR space removal capacity
  • Examples of the chemical adsorbent include hydrazide compounds such as adipic acid dihydrazide, dodecanedioic acid dihydrazide, and succinate dihydrazide, which are primary to tertiary amine compounds, p-aminobenzenesulfonic acid, ethylene urea condensate, and tris ( Hydroxylmethyl) aminomethane and the like.
  • adipic acid dihydrazide is preferable in terms of adsorption performance of aldehydes.
  • porous bodies include activated carbon, porous silica, zeolite, sepiolite, active alumina, aluminum silicate, silica gel, alumina gel, activated clay, layered compounds such as zirconium phosphate and ammonium polytriphosphate, and inorganics such as porous clay minerals. Particles can be mentioned and can be selected from these according to the purpose. Among them, porous silica is preferable because it can be procured at low cost.
  • the content of the chemical adsorbent in the gas adsorbent is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more. ..
  • the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less.
  • the gas adsorbent of the present invention preferably has a toluene desorption rate of 25% or less after saturated adsorption of toluene.
  • the gas adsorbent of the present invention having a toluene desorption rate of 25% or less after saturated adsorption of toluene has an odor such as toluene once adsorbed on the air filter in an air filter using this gas adsorbent. Desorption of components from the air filter can be suppressed.
  • the saturated adsorption of toluene means a state in which toluene is adsorbed on the gas adsorbent as described in "(1) Saturated adsorption amount of toluene (g / m 2 )" in the section of Examples described later. ..
  • toluene desorption rate is measured by the method described in "(2) Toluene desorption rate (%)" in the section of Examples described later.
  • the amount of toluene adsorbed in the saturated adsorption state relates to the life of the above-mentioned physical adsorption characteristics for organic gas, such as the ability to remove tobacco odor when a gas adsorbent is used as an air filter.
  • the saturated adsorption amount of toluene is preferably 10 g / m 2 or more by the measuring method described in "(1) Saturated adsorption amount of toluene (g / m 2 )" in the section of Examples described later. More preferably, it is 20 g / m 2 or more.
  • the gas adsorbent in the present invention is preferably used after being formed in a sheet shape. That is, the gas adsorbent of the present invention is suitably used for a gas adsorbent sheet.
  • the fact that the gas adsorbent is formed in the form of a sheet means that the gas adsorbent particles are dispersed between the fibers or sandwiched between the laminated non-woven fabrics, and the dust collecting performance of the fiber sheet is maintained. , Deodorizing performance can be added.
  • a gas adsorbent and a heat-adhesive fiber mixed and dispersed are suction-laminated on a base material non-woven fabric on a collection net, then fused and integrated in a heating furnace and heated. It is possible to adopt the so-called air-laid method in which the cover non-woven fabric is bonded at the furnace outlet.
  • gas adsorbent particles and powdered heat-adhesive resin particles are quantitatively and uniformly sprayed on the base non-woven fabric, the heat-adhesive resin particles are heated and melted by a heater, and then the cover non-woven fabric is laminated and pressure-bonded.
  • Examples include, but are limited to, a method of integrating by spraying gas adsorbent particles on the base non-woven fabric while spraying a heated molten resin, and then laminating and pressure-bonding the cover non-woven fabric. It's not a thing.
  • the texture of the gas adsorbent is preferably in the range of 15 to 400 g / m 2 , and by setting it in the range of 30 to 300 g / m 2 , the gas It is more preferable because it has a high adsorption capacity and is excellent in pleating (bending) workability when processing the obtained sheet-shaped filter medium into an air filter.
  • the shape of the gas adsorbent is not particularly limited, and examples thereof include a spherical shape, a plate shape, a polygonal shape, an indefinite shape, and the like, and any known shape such as a crushed one or a molded one can be arbitrarily selected.
  • the size of the gas adsorbent is not particularly specified, but it is recommended to use a granular gas adsorbent having an average particle diameter of 50 to 400 ⁇ m when processing the filter medium after forming it into a sheet into an air filter. It is preferable because it has excellent workability.
  • the average particle size referred to here is a particle corresponding to the size of a sieve through which 50% by mass of the total mass of the granular gas adsorbent is measured by measuring the particle size distribution by JIS-Z-8815 (1994). The diameter.
  • the gas adsorbent in the present invention is preferably used for a filter medium.
  • the filter medium has two or more layers of a non-woven fabric and the gas adsorbent of the present invention, and the gas adsorbent of the present invention is applied to at least one of one or more layers formed by the two or more layers of the non-woven fabric. Be retained.
  • the above filter medium can be suitably used for an air filter.
  • the form of the non-woven fabric is not particularly limited, and examples thereof include chemical-bonded non-woven fabrics, wet papermaking non-woven fabrics, spunbonded non-woven fabrics, melt-blown non-woven fabrics, spunlaced non-woven fabrics, and air-laid non-woven fabrics.
  • the non-woven fabric provided in the above filter medium is preferably an electret non-woven fabric.
  • the electret non-woven fabric is preferable because the above-mentioned filter medium can collect dust in the air with higher efficiency.
  • the electret non-woven fabric can be obtained by subjecting the non-woven fabric to electret processing.
  • the electret processing is a process of imparting an electric charge to the non-woven fabric and imparting the property of collecting dust in the air to the non-woven fabric by the electrostatic force.
  • the method of applying electric charge is not particularly specified, and a method such as a corona discharge method, a hydrocharge method, or a triboelectric charge method can be adopted for the non-woven fabric, and a higher charge amount among them. From the viewpoint of obtaining the above, it is preferable to use the hydrocharge method by the pure water suction method.
  • a particulate gas adsorbent is uniformly mixed with an adhesive powder that adheres by heat, such as a polyethylene resin having a particle size equivalent to that of the gas adsorbent (hereinafter, may be referred to as a gas composite adsorbent).
  • an adhesive powder that adheres by heat such as a polyethylene resin having a particle size equivalent to that of the gas adsorbent (hereinafter, may be referred to as a gas composite adsorbent).
  • a method in which another non-woven fabric is laminated on the gas adsorbent spraying surface to obtain a laminated body, and the laminated body is passed between nip rolls set at predetermined intervals to be laminated is preferably used.
  • the amount of the gas adsorbent sprayed here is preferably in the range of 15 to 400 g / m 2 .
  • the thickness of the non-woven fabric is preferably 0.08 to 0.60 mm from the viewpoint of having a certain strength and increasing the area that can be accommodated in a certain volume when pleated, and the lower limit thereof is 0. It is more preferably .15 mm or more, and the upper limit thereof is more preferably 0.50 mm or less.
  • the above-mentioned filter medium has two or more layers of non-woven fabric, and the thickness of these non-woven fabrics may be the same or different.
  • thermoplastic resin capable of melt spinning examples include polyester, polyamide, polyolefin, acrylic, vinylon, polystyrene, polyvinyl chloride, polyvinylidene chloride, polylactic acid, and the like, which can be selected according to the intended use. Further, a plurality of types may be used in combination.
  • a material having a high electric resistance such as a polyolefin resin such as polypropylene, polyethylene and polystyrene, an aromatic polyester resin such as polyethylene terephthalate or a polycarbonate resin is preferable.
  • the filter medium provided with the gas adsorbent of the present invention can be suitably used for an air filter.
  • the air filter is formed by fixing the four sides of the pleated filter medium and the outer frame.
  • the above-mentioned filter medium forms a three-dimensional shape having peaks and valleys in a pleated state.
  • the pleating process is a process in which the above-mentioned filter medium is folded into a mountain valley shape at a predetermined folding height in a certain direction, and a method such as a reciprocating type or a rotary type can be used as the folding method. By pleating, it is possible to obtain an air filter in which a larger area of filter media is placed in a fixed volume as an air filter.
  • a separator can be provided in the space generated between the adjacent mountains.
  • a separator can be provided in the space generated between the adjacent mountains.
  • an outer frame is attached to the outer circumference of the pleated filter medium for the purpose of molding into a predetermined size.
  • a flat non-woven fabric coated with an adhesive such as a polyolefin hot melt is pasted on the four outer peripheral sides of the pleated filter medium to form a rectangular parallelepiped air filter. The method can be mentioned.
  • an electret melt blown non-woven fabric (with a basis weight of 30 g / m 2 ) is laminated on the spray surface, and then pressed by a nip roll to form a sheet having a predetermined thickness.
  • a filter medium was obtained.
  • the obtained measured value was defined as m2 (g).
  • the toluene adsorption capacity per unit area of the filter medium was calculated from the following formula, and the saturated adsorption amount of toluene per 40 g / m 2 of the gas adsorbent was determined.
  • Toluene adsorption capacity (g / m 2 ) (m2-m1) / (0.1 * 0.1)
  • Toluene desorption rate (%) A circular filter medium sample (area 28.3 cm 2 ) having a diameter of 6 cm was collected from the filter medium after measuring the saturated adsorption amount of toluene described in (1) above. Two cylindrical wind tunnels having a ventilation diameter of 4 cm and a body length of 15 cm were prepared, and each was attached to one side and the other side of the filter medium sample. Next, air having a temperature of 20 ° C. and a humidity of 50% RH was passed from one surface side of the filter medium sample to the other surface side at a wind speed of 0.06 m / sec.
  • the toluene concentration (ppm) of the air on the downstream side of the filter medium sample is measured by an infrared absorption type gas densitometer (manufactured by Nippon Thermo Co., Ltd.). MIRAN SapphlRe) was used to measure for 5 minutes at 2-second intervals, and the integrated desorption amount of toluene was measured from the detected concentration of toluene in the air. From the obtained measurement results, toluene per unit area (1 m 2 ) was measured. The cumulative desorption amount (g / m 2 ) of was calculated.
  • Formaldehyde spatial purification capacity (m 3 / hr)
  • a polyolefin resin manufactured by Hitachi Chemical Polymer Co., Ltd.
  • Hybon 9500 was applied in succession using a compression nozzle to a thickness of 3 mm and at intervals of 5 cm in the filter medium width direction, and then folded again according to the creases of the pleating process, and the distance between adjacent pleats was 5
  • the linear hot-melt resins were adhered and fixed to each other so as to have a thickness of 0.6 mm, and a substantially rectangular pleated filter medium was obtained.
  • a polyolefin adhesive (Hybon YH450-1 manufactured by Hitachi Kasei Polymer Co., Ltd.) heated and melted at 200 ° C.
  • the air purifier after collecting the cigarette combustion smoke was left for 24 hours without operating in a test room having a volume of 30 m 3 , and then the air purifier was operated to check the odor intensity and the degree of comfort and discomfort of the discharged air. , 5 panelists scored according to the criteria shown in Tables 3 and 4, and the average value was calculated.
  • Example 1 Only granular activated carbon (CN360S manufactured by Futamura Chemical Co., Ltd.) (constituent material 1 of the gas adsorbent) was used as the gas adsorbent.
  • a filter medium having the above gas adsorbent was produced by the method described in the above [Method for producing a filter medium using a gas adsorbent]. The thickness of this filter medium was 0.9 mm. Further, the obtained filter medium was pleated, and outer frames were attached to the four sides of the pleated filter medium to obtain an air filter.
  • Table 1 summarizes the granular activated carbon used in the gas adsorbent of Example 1, the gas adsorbent of Example 1, and the air filter using the gas adsorbent of Example 1.
  • Example 2 Only granular activated carbon (Kuraray Coal (registered trademark) GW30 / 60D) (constituent material 1 of the gas adsorbent) was used as the gas adsorbent.
  • a filter medium having the above gas adsorbent was produced by the method described in the above [Method for producing a filter medium using a gas adsorbent]. The thickness of this filter medium was 0.9 mm. Further, the obtained filter medium was pleated, and outer frames were attached to the four sides of the pleated filter medium to obtain an air filter.
  • Table 1 summarizes the granular activated carbon used in the gas adsorbent of Example 2, the gas adsorbent of Example 2, and the air filter using the gas adsorbent of Example 2.
  • Example 3 Porous silica particles (Fuji Silicia) impregnated with the same activated carbon (constituent material 1 of the gas adsorbent) used for the gas adsorbent of Example 2 and dihydrazide adipate (manufactured by Nippon Kasei Co., Ltd.) as a chemical adsorbent.
  • SYLYSIA CARIACT G-6 manufactured by Kagaku Co., Ltd.
  • a filter medium having the above gas adsorbent was produced by the method described in the above [Method for producing a filter medium using a gas adsorbent].
  • This filter medium was 1.0 mm. Further, the obtained filter medium was pleated, and outer frames were attached to the four sides of the pleated filter medium to obtain an air filter.
  • Table 1 summarizes the granular activated carbon used in the gas adsorbent of Example 3, the gas adsorbent of Example 3, and the air filter using the gas adsorbent of Example 3.
  • Example 4 The same activated carbon used for the gas adsorbent of Example 3 (constituent material 1 of the gas adsorbent) and the same chemical adsorbent used for the gas adsorbent of Example 3 (constituent material 2 of the gas adsorbent).
  • a gas adsorbent prepared in a ratio of activated carbon: chemical adsorbent 3:10 (mass ratio) was used.
  • the content of adipic acid dihydrazide in the above chemical adsorbent was 9% by mass with respect to the total amount of the chemical adsorbent.
  • a filter medium having the above gas adsorbent was produced by the method described in the above [Method for producing a filter medium using a gas adsorbent].
  • the thickness of this filter medium was 1.0 mm.
  • the obtained filter medium was pleated, and outer frames were attached to the four sides of the pleated filter medium to obtain an air filter.
  • Table 1 summarizes the granular activated carbon used in the gas adsorbent of Example 4, the gas adsorbent of Example 4, and the air filter using the gas adsorbent of Example 4.
  • Examples 1 and 2 since toluene saturation adsorption is high and toluene desorption rate is low, secondary odor is less generated after tobacco odor adsorption when processed into a filter and mounted on an air purifier. It was an air filter that did not make the user feel uncomfortable. Further, in Examples 3 and 4, the space purification capacity (CADR) for formaldehyde gas can be maintained for a long period of time.
  • CIR space purification capacity
  • Comparative Example 3 has a high toluene desorption rate after saturated adsorption of toluene. Therefore, when the gas component was processed into a filter and mounted on an air purifier, the amount of re-emission of the gas component after adsorption of the tobacco odor increased, the intensity of the secondary odor was strong, and an odor with a high degree of discomfort was felt. This is because the pore volume of the activated carbon used as the gas adsorbent is small, and the pore volume formed by the pores of 0.4 to 2 nm calculated by the MP method, which is effective in reducing the secondary odor, is particularly large. It is considered that the amount of high molecular weight gas having low adsorption performance is likely to be re-emitted with respect to various odorous gases in tobacco odor.
  • the pores existing in the activated carbon are divided into pores having a pore diameter of 0.4 to 2 nm calculated by the MP method and pores having a pore diameter of more than 2 nm calculated by the BJH method. Since the activated carbon contained in the gas adsorbent of Comparative Example 4 has a pore volume of 51% of pores having a pore diameter of 0.4 to 2 nm calculated by the MP method, all the pores of the above activated carbon are fine. It can be said that 49% of the pore volume is due to the pores having a pore diameter of more than 2 nm calculated by the BJH method.
  • the activated carbon contained in the gas adsorbent of Comparative Example 4 has many large pores having a pore diameter of more than 2 nm calculated by the BJH method, and one of these large pores has one. It is considered that the tobacco odor adsorbed on the activated carbon is easily re-emitted because the contact area with air per pore becomes large.
  • the gas adsorbent according to the present invention is mainly mounted on a household air purifier and is used for an air filter and a filter medium for purifying indoor air.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)

Abstract

The purpose of the invention is to provide: a gas adsorbent that has excellent capacity to adsorb a gas component and has little odor re-emission after being used as an air filter; filter material for an air filter; and an air filter. This gas adsorbent contains activated charcoal. The activated charcoal has a pore volume of pores with a pore size of 0.4 to 2 nm in the range of 0.40 to 0.55 cc/g as calculated by the MP method, and that pore volume is 75% or more of the pore volume for all pores in the activated charcoal as calculated by the MP method and the BJH method.

Description

ガス吸着剤Gas adsorbent
　本発明は、ガス吸着剤に関する。 The present invention relates to a gas adsorbent.
　家庭内における粉塵や臭気ガス成分を除去する目的で空気清浄機が使用されている。近年、家庭用空気清浄機の脱臭機能に対する要求性能として、空気清浄機を使用する居住環境で発生する揮発性有機化合物（ＶＯＣ）、ホルムアルデヒド等の様々なガスに対する脱臭性能が求められる。中でもＶＯＣについては、人体への好ましくない影響が示されており、ＶＯＣの室内環境濃度を一定以下に管理することが各国の法令、省令で定められている。空気清浄機はこのＶＯＣに対する除去機器としての性能が期待されている。また、空気清浄機には、シックハウス症候群の原因とされる壁紙等の建築材料中から放出されるリスクのある、ホルムアルデヒドに対する除去効率の高さと、その長寿命化が求められている。ホルムアルデヒドに対する除去効率の高さとは、所定空間内のガス濃度を下げるのに要する、空気清浄機の運転時間が短いことを示す。ホルムアルデヒドに対する除去効率の長寿命化とは、所定量のホルムアルデヒドガスを吸着した後でも、上記のホルムアルデヒドに対する除去効率が維持されることである。ホルムアルデヒドに対する除去効率は空間浄化能力（ＣＡＤＲ：Ｃｌｅａｎ　Ａｉｒ　Ｄｅｌｉｖｅｒｙ　Ｒａｔｅ）、ホルムアルデヒドに対する除去効率の寿命は累積浄化量（ＣＣＭ：Ｃｕｍｕｌａｔｅ　Ｃｌｅａｎ　Ｍａｓｓ）として評価基準がＧＢ／Ｔ　１８８０１　２０１５（中国国家基準）等で示されている。 An air purifier is used for the purpose of removing dust and odorous gas components in the home. In recent years, as a required performance for the deodorizing function of a household air purifier, deodorizing performance for various gases such as volatile organic compounds (VOC) and formaldehyde generated in a living environment where the air purifier is used is required. Among them, VOCs have been shown to have unfavorable effects on the human body, and it is stipulated by the laws and ministerial ordinances of each country to control the indoor environmental concentration of VOCs below a certain level. The air purifier is expected to perform as a removal device for this VOC. In addition, air purifiers are required to have high removal efficiency for formaldehyde, which has a risk of being released from building materials such as wallpaper, which is a cause of sick house syndrome, and to extend its life. The high removal efficiency for formaldehyde means that the operating time of the air purifier required to reduce the gas concentration in the predetermined space is short. Prolonging the life of the removal efficiency for formaldehyde means that the removal efficiency for formaldehyde is maintained even after adsorbing a predetermined amount of formaldehyde gas. The removal efficiency for formaldehyde is the space purification capacity (CADR: Clean Air Delivery Rate), and the life of the removal efficiency for formaldehyde is the cumulative purification amount (CCM: Cumulate Clean Mass). It is shown.
　これらの要求性能を満足するために、空気清浄機に用いられるエアフィルターとして、活性炭、およびホルムアルデヒドと化学反応性により吸着する吸着剤の混合物を、エレクトレット加工された不織布からなる集塵シートと補強シート間に挟み込んだ構成による集塵脱臭濾材を備えるものが提案されている（例えば、特許文献１参照）。 In order to satisfy these required performances, as an air filter used in an air purifier, a dust collection sheet and a reinforcing sheet made of an electret-processed non-woven fabric are mixed with activated carbon and an adsorbent that adsorbs with formaldehyde by chemical reactivity. A device including a dust collecting and deodorizing filter medium having a structure sandwiched between them has been proposed (see, for example, Patent Document 1).
　また、吸着剤には活性炭が含まれ、活性炭はブタンやトルエンなどの臭気成分を吸着除去することが期待されている。そして、活性炭は多数の細孔を備えており、これらの細孔がどのようなものであるかによって活性炭によるｎ－ブタンの吸着除去の効率が変化することが知られている。具体的には、活性炭のＭＰ法で算出される細孔直径が０．６５ｎｍ以下の細孔容積が０．１ｃｃ／ｇ以上であることで、この活性炭を含む吸着剤のｎ－ブタンの吸着除去の効率が向上することが知られている（例えば、特許文献２参照）。 In addition, the adsorbent contains activated carbon, and the activated carbon is expected to adsorb and remove odorous components such as butane and toluene. It is known that activated carbon has a large number of pores, and the efficiency of adsorption and removal of n-butane by activated carbon changes depending on what these pores are. Specifically, when the pore diameter of 0.65 nm or less calculated by the MP method of activated carbon is 0.1 cc / g or more, the adsorption removal of n-butane of the adsorbent containing this activated carbon It is known that the efficiency of the above is improved (see, for example, Patent Document 2).
日本国特開２０１５－２９７７０号公報Japanese Patent Application Laid-Open No. 2015-29770 日本国特開平１１－２２６３９３号公報Japanese Patent Application Laid-Open No. 11-226393
　しかしながら、発明者らの知見によると、実際に上記した設計思想に基づいて得られたエアフィルターを空気清浄機に搭載したところ、一定期間使用したエアフィルターから、該エアフィルターに一旦吸着された臭気成分が脱離して空間に放出される（二次発臭）問題が発生する。具体的には、一旦、エアフィルターに吸着されたトルエンなどの臭気成分がエアフィルターから脱離して空間に放出されるのである。そして、この問題は、主に上記のエアフィルターに用いられる吸着剤によるものと考える。ここで、特許文献２には、ＭＰ法で算出される細孔直径が０．６５ｎｍ以下の細孔容積が０．１ｃｃ／ｇ以上である活性炭を含む吸着剤が開示されている。さらに、特許文献２には、上記の活性炭を含む吸着剤は、低融点かつ無極性の低分子量脂肪族炭化水素であるｎ－ブタン等の吸着除去の効率が優れたものとなることが開示されている。しかし、その一方で、特許文献２には、上記の吸着剤で、一旦、エアフィルターに吸着されたｎ－ブタンのエアフィルターからの脱離が抑制されることについては何ら開示されていない。当然、特許文献２には、上記の吸着剤で、一旦、エアフィルターに吸着されたトルエンなどの芳香族炭化水素のエアフィルターからの脱離が抑制されることについても何ら開示されていない。 However, according to the findings of the inventors, when an air filter actually obtained based on the above design concept is mounted on an air purifier, the odor once adsorbed on the air filter from the air filter used for a certain period of time There is a problem that the components are desorbed and released into the space (secondary odor). Specifically, odorous components such as toluene once adsorbed on the air filter are separated from the air filter and released into the space. And it is considered that this problem is mainly due to the adsorbent used in the above-mentioned air filter. Here, Patent Document 2 discloses an adsorbent containing activated carbon having a pore diameter of 0.65 nm or less and a pore volume of 0.1 cc / g or more calculated by the MP method. Further, Patent Document 2 discloses that the above-mentioned adsorbent containing activated carbon has excellent efficiency in adsorbing and removing n-butane, which is a low molecular weight aliphatic hydrocarbon having a low melting point and no polarity. ing. However, on the other hand, Patent Document 2 does not disclose at all that the above-mentioned adsorbent suppresses the desorption of n-butane once adsorbed on the air filter from the air filter. Naturally, Patent Document 2 does not disclose at all that the above-mentioned adsorbent suppresses the desorption of aromatic hydrocarbons such as toluene once adsorbed on the air filter from the air filter.
　そこで、本発明は、上記の事情に鑑み、一旦、エアフィルターに吸着されたトルエンなどの臭気成分のエアフィルターからの脱離を抑制できる、すわなち、二次発臭を抑制できるガス吸着剤を提供することを課題とする。 Therefore, in view of the above circumstances, the present invention is a gas adsorbent capable of suppressing desorption of odorous components such as toluene once adsorbed on the air filter from the air filter, that is, suppressing secondary odor. The challenge is to provide.
　上記課題を解決する本発明のガス吸着剤は、活性炭を含むガス吸着剤であって、
上記活性炭の、ＭＰ法により算出される、細孔径が０．４～２ｎｍの細孔の細孔容積が０．４０～０．５５ｃｃ／ｇの範囲であり、かつ、上記細孔容積は、ＭＰ法およびＢＪＨ法により算出される、上記活性炭の全細孔の細孔容積に対する比率が７５％以上である。
　本発明のガス吸着剤は、以下の（１）～（３）のいずれか１つの特徴を有することが好ましい。
（１）上記活性炭の含有量が、上記ガス吸着剤の全体に対し、２０質量％以上である。
（２）さらに、化学反応によりアルデヒドを吸着する化学吸着剤を含む。
（３）トルエン飽和吸着後の脱離率が２５％以下である。
　本発明のガス吸着シートは、本発明のガス吸着剤を含んでいる。
　本発明の濾材は、本発明のガス吸着剤が、２層以上の不織布により形成される１つ以上の層間の少なくとも１つに保持されている。
　本発明のエアフィルターは本発明の濾材を備えている。 The gas adsorbent of the present invention that solves the above problems is a gas adsorbent containing activated carbon.
The pore volume of the activated carbon having a pore diameter of 0.4 to 2 nm calculated by the MP method is in the range of 0.40 to 0.55 cc / g, and the pore volume is MP. The ratio of the activated carbon to the pore volume of all pores calculated by the method and the BJH method is 75% or more.
The gas adsorbent of the present invention preferably has any one of the following characteristics (1) to (3).
(1) The content of the activated carbon is 20% by mass or more with respect to the total of the gas adsorbent.
(2) Further, it contains a chemical adsorbent that adsorbs aldehyde by a chemical reaction.
(3) The desorption rate after saturated adsorption of toluene is 25% or less.
The gas adsorbent sheet of the present invention contains the gas adsorbent of the present invention.
In the filter medium of the present invention, the gas adsorbent of the present invention is held in at least one of one or more layers formed by two or more layers of non-woven fabric.
The air filter of the present invention includes the filter medium of the present invention.
　本発明によれば、一旦、エアフィルターに吸着されたトルエンなどの臭気成分のエアフィルターからの脱離を抑制することができる、すわなち、二次発臭を抑制することができる吸着剤を提供することができる。 According to the present invention, an adsorbent capable of suppressing desorption of odorous components such as toluene once adsorbed on the air filter from the air filter, that is, capable of suppressing secondary odor. Can be provided.
　本発明は、前記課題、すなわち、一旦、エアフィルターに吸着されたトルエンなどの臭気成分のエアフィルターからの脱離を抑制することができる、すわなち、二次発臭を抑制することができる吸着剤を提供することについて鋭意検討した結果、到達したものである。以下、本発明について詳細に説明する。
　なお、本明細書において、「質量」は「重量」と同義である。 The present invention can suppress the above-mentioned problem, that is, the desorption of odorous components such as toluene once adsorbed on the air filter from the air filter, that is, the secondary odor can be suppressed. This was achieved as a result of diligent studies on providing an adsorbent. Hereinafter, the present invention will be described in detail.
In addition, in this specification, "mass" is synonymous with "weight".
　まず、本発明のガス吸着剤は、活性炭を含む。そして、本発明のガス吸着剤が含む活性炭は、以下の細孔構造を有するものである。すなわち、上記の活性炭が有する細孔構造は、活性炭の、ＭＰ法により算出される、細孔径が０．４～２ｎｍの細孔の細孔容積が０．４０～０．５５ｃｃ／ｇの範囲であり、かつ、上記細孔容積が、ＭＰ法およびＢＪＨ法により算出される、上記活性炭の全細孔の細孔容積に対する比率が７５％以上である。 First, the gas adsorbent of the present invention contains activated carbon. The activated carbon contained in the gas adsorbent of the present invention has the following pore structure. That is, the pore structure of the above activated carbon is such that the pore volume of the pores having a pore diameter of 0.4 to 2 nm calculated by the MP method of the activated carbon is in the range of 0.40 to 0.55 cc / g. Yes, and the pore volume is calculated by the MP method and the BJH method, and the ratio of the activated carbon to the pore volume of all pores is 75% or more.
　このように、活性炭が備える細孔のうち、特定のサイズの細孔（細孔径が０．４～２ｎｍの範囲である細孔）が形成する細孔容積が特定の範囲（０．４０～０．５５ｃｃ／ｇ）であり、すなわち、特定のサイズの細孔が活性炭に特定の数、存在し、さらに、細孔径が０．４～２ｎｍの細孔の細孔容積の、全細孔の細孔容積に対する比率が７５％以上、すなわち、細孔径が０．４ｎｍ未満の細孔の細孔容積および細孔径が２ｎｍを超える細孔の細孔容積の合計の全細孔の細孔容積に対する比率が２５％以下であることで、この活性炭を有するガス吸着剤は、トルエンなどの臭気成分の吸着除去の性能に優れ、さらに、一旦、吸着したトルエンなどの臭気成分のガス吸着剤からの脱離が抑制される。 As described above, among the pores contained in the activated carbon, the pore volume formed by the pores of a specific size (pores having a pore diameter in the range of 0.4 to 2 nm) is in a specific range (0.40 to 0). .55 cc / g), that is, there are a specific number of pores of a specific size in the activated carbon, and the pore volume of the pores having a pore diameter of 0.4 to 2 nm is fine. The ratio to the pore volume is 75% or more, that is, the ratio of the pore volume of the pores having a pore diameter of less than 0.4 nm and the pore volume of the pores having a pore diameter of more than 2 nm to the total pore volume. When the amount is 25% or less, the gas adsorbent having activated carbon is excellent in the performance of adsorbing and removing odorous components such as toluene, and further, once adsorbed, the odorous components such as toluene are desorbed from the gas adsorbent. Is suppressed.
　この効果が得られるメカニズムについては以下のとおりと推測する。すなわち、活性炭に存在する細孔のうち、細孔径が０．４～２ｎｍの細孔はトルエンなどの臭気成分の吸着除去の性能に優れ、さらに、この細孔内に、一旦、吸着されたトルエンなどの臭気成分は、この細孔内から脱離し難いとの特徴を有する。その一方で、細孔径が０．４ｎｍ未満の細孔はトルエンなどの臭気成分、特に分子量の大きい臭気成分の吸着除去の性能に劣り、細孔径が２ｎｍを超える細孔は細孔内に吸着されたトルエンなどの臭気成分の脱離を抑制する性能（以下、脱離抑制性能とすることがある）に劣ると推測する。そして、活性炭の、ＭＰ法により算出される、細孔径が０．４～２ｎｍの細孔の細孔容積が０．４０～０．５５ｃｃ／ｇの範囲であり、かつ、上記細孔容積の、ＭＰ法およびＢＪＨ法により算出される上記活性炭の全細孔の細孔容積に対する比率が７５％以上である細孔構造は、臭気成分の吸着除去の性能および脱離抑制性能に優れる細孔を特定の量、有し、さらに、活性炭に存在する全ての細孔の量に対する臭気成分の吸着除去の性能および脱離抑制性能に優れる細孔の量の比率が特定以上である、すなわち、臭気成分の吸着除去の性能に劣る細孔または脱離抑制性能に劣る細孔の合計の量が特定以下である細孔構造であるといえる。このことにより、この活性炭を有するガス吸着剤の臭気成分の吸着除去の性能および脱離抑制性能がともに優れたものとなると推測する。 The mechanism by which this effect can be obtained is presumed to be as follows. That is, among the pores existing in the activated carbon, the pores having a pore diameter of 0.4 to 2 nm are excellent in the performance of adsorbing and removing odorous components such as toluene, and further, toluene once adsorbed in these pores. Odor components such as these have the characteristic that they are difficult to desorb from the pores. On the other hand, pores having a pore diameter of less than 0.4 nm are inferior in adsorption and removal performance of odorous components such as toluene, especially odorous components having a large molecular weight, and pores having a pore diameter of more than 2 nm are adsorbed in the pores. It is presumed that the performance of suppressing the desorption of odorous components such as toluene (hereinafter, may be referred to as the desorption suppressing performance) is inferior. Then, the pore volume of the pores having a pore diameter of 0.4 to 2 nm calculated by the MP method of the activated carbon is in the range of 0.40 to 0.55 cc / g, and the pore volume is the above. The pore structure in which the ratio of the activated carbon to the pore volume of the total pores calculated by the MP method and the BJH method is 75% or more identifies pores having excellent adsorption removal performance and desorption suppression performance of odorous components. The ratio of the amount of pores having excellent adsorption removal performance and desorption suppressing performance of odorous components to the amount of all pores present in activated carbon is more than a specific value, that is, of the odorous components. It can be said that the pore structure has a pore structure in which the total amount of pores inferior in adsorption removal performance or pores inferior in desorption suppressing performance is less than a specific value. As a result, it is presumed that the performance of adsorbing and removing the odorous component of the gas adsorbent having activated carbon and the performance of suppressing desorption are both excellent.
　ＭＰ（ＭＩＣＲＯＰＯＲＥ）法は活性炭が備える細孔の細孔径における分布を定量化することができる解析法である。また、一般的に、活性炭が備える細孔径の細孔直径および細孔容積の解析法としては、ＭＰ（ＭＩＣＲＯＰＯＲＥ）法や、ＢＪＨ（Ｂａｒｒｅｔｔ－Ｊｏｙｎｅｒ－Ｈａｌｅｎｄａ）法などがある。本発明では、活性炭が備える細孔のうち、毛管凝縮が起こらない細孔径が０．４～２ｎｍのミクロ孔の解析にはＭＰ法を採用した。また、本発明では、活性炭が備える細孔のうち、細孔径が２ｎｍ以上のマクロ孔の解析にはＢＪＨ法を採用した。ここで、本発明におけるＭＰ法およびＢＪＨ法により算出される活性炭の全細孔の細孔容積とは、ＭＰ法で得られた細孔容積の値とＢＪＨ法で得られた細孔容積の値の合計値をいう。 The MP (MICROPORE) method is an analysis method that can quantify the distribution of pores in activated carbon in the pore size. In general, as a method for analyzing the pore diameter and the pore volume of the activated carbon, there are an MP (MICROPORE) method, a BJH (Barrett-Joiner-Halenda) method, and the like. In the present invention, among the pores contained in activated carbon, the MP method was adopted for the analysis of micropores having a pore diameter of 0.4 to 2 nm in which capillary condensation does not occur. Further, in the present invention, the BJH method was adopted for the analysis of macropores having a pore diameter of 2 nm or more among the pores contained in the activated carbon. Here, the pore volume of the total pores of the activated carbon calculated by the MP method and the BJH method in the present invention is the value of the pore volume obtained by the MP method and the value of the pore volume obtained by the BJH method. Refers to the total value of.
　上記のような細孔構造を有する活性炭は、原料として、ヤシ殻、石炭ピッチ、フェノール樹脂など公知のものから任意に選択でき、水蒸気による高温処理や、塩酸等の薬品処理によって細孔を形成する賦活条件を調整することによって得られる。中でもヤシ殻を原料とし、水蒸気による賦活方法を選択することで、細孔サイズが０．４～２ｎｍの範囲のミクロ孔が形成された活性炭が得られやすいため、より好ましい。 Activated carbon having the above-mentioned pore structure can be arbitrarily selected from known materials such as coconut shell, coal pitch, and phenol resin as a raw material, and pores are formed by high-temperature treatment with steam or chemical treatment with hydrochloric acid or the like. Obtained by adjusting the activation conditions. Above all, it is more preferable to use coconut shell as a raw material and select an activation method using steam because activated carbon having micropores having a pore size in the range of 0.4 to 2 nm can be easily obtained.
　従って、ガス吸着後の二次発臭低減の両立には、ガス吸着剤に用いる活性炭の細孔構造を制御し、臭気成分の吸着に適したものを得ることが必要であることを見出し、上記の発明に至った。 Therefore, it has been found that in order to achieve both reduction of secondary odor after gas adsorption, it is necessary to control the pore structure of the activated carbon used as the gas adsorbent to obtain one suitable for adsorption of odorous components. It led to the invention of.
　本発明のガス吸着剤における活性炭の含有量は、ガス吸着剤全体に対し、２０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることがさらに好ましい。活性炭の含有量が、ガス吸着剤全体に対し、２０質量％以上であることで、ガス吸着剤のトルエンの飽和吸着量およびトルエンの脱離率がより優れたものとなる。ガス吸着剤における活性炭の含有量の上限は特に限定されず、１００質量％であってもよいが、例えば９０質量％以下であってもよく、５０質量％以下であってもよい。 The content of activated carbon in the gas adsorbent of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more with respect to the entire gas adsorbent. preferable. When the content of the activated carbon is 20% by mass or more with respect to the entire gas adsorbent, the saturated adsorption amount of toluene of the gas adsorbent and the desorption rate of toluene become more excellent. The upper limit of the content of activated carbon in the gas adsorbent is not particularly limited and may be 100% by mass, but may be, for example, 90% by mass or less, or 50% by mass or less.
　本発明のガス吸着剤は、活性炭以外に、ガス吸着剤の構成材料として、空気中のガス成分との接触により発生する分子間引力等の作用で、構成材料表面上にガスを濃縮させて保持する物理吸着剤、もしくは、ガス成分との化学反応により分子構造を変化させることで、実質的にガス成分の空間濃度を下げる作用を有する化学吸着剤を含むことができる。ここで、物理吸着剤としては、ゼオライト、セピオライト等の多孔質物質からなる物理吸着剤から任意に選択することができる。化学吸着剤としては活性炭、ゼオライト等の多孔質物質を担持体とし、この担持体にリン酸、塩酸等の酸成分を添着させることで得られる対アルカリ成分ガス吸着剤や、この担持体に炭酸水素ナトリウム、炭酸カリウム等のアルカリ成分を添着させることで得られる対酸成分ガス吸着剤、第１級から第３級アミン化合物成分を添着させることで得られるアルデヒドガス吸着剤などから、任意に選択することができる。 In addition to activated carbon, the gas adsorbent of the present invention concentrates and retains gas on the surface of the constituent material by the action of intermolecular attractive force generated by contact with a gas component in the air as a constituent material of the gas adsorbent. By changing the molecular structure by a chemical reaction with a gas component, it is possible to include a physical adsorbent that substantially lowers the spatial concentration of the gas component. Here, the physical adsorbent can be arbitrarily selected from a physical adsorbent made of a porous substance such as zeolite or sepiolite. As the chemical adsorbent, a porous substance such as activated carbon or zeolite is used as a support, and an acid component such as phosphoric acid or hydrochloric acid is impregnated to the support to obtain an alkali component gas adsorbent, or carbon dioxide is added to the support. Arbitrarily selected from acid component gas adsorbents obtained by impregnating alkaline components such as sodium hydrogen and potassium carbonate, and aldehyde gas adsorbents obtained by impregnating primary to tertiary amine compound components. can do.
　なかでも、本発明のガス吸着剤は、化学反応によりアルデヒドを吸着する化学吸着剤を含むことが好ましい。本発明のガス吸着剤が、化学反応によりアルデヒドを吸着する化学吸着剤を含むことで、ホルムアルデヒドの吸着容量を向上させることができ、かつ、ガス吸着後の脱離が少ないため、空気清浄機として使用した際、ホルムアルデヒドの空間除去能力（ＣＡＤＲ）の低下を抑えることができるため好ましい。化学吸着剤としては、第１級から第３級アミン化合物であるアジピン酸ジヒドラジド、ドデカン二酸ジヒドラジド、コハク酸ジヒドラジドなどのヒドラジド化合物や、ｐ－アミノベンゼンスルホン酸、エチレン尿素縮合体薬剤、トリス（ヒドロキシメチル）アミノメタンなどが挙げられる。とりわけ、アジピン酸ジヒドラジドがアルデヒド類の吸着性能の点で好ましい。また、化学吸着剤の構造として、上記の化学吸着剤を多孔質体（多孔質物質からなる担持体）の表面に担持させることにより、アルデヒドガスとの接触効率を高めることができるためより好ましい。多孔質体としては、活性炭や、多孔質シリカ、ゼオライト、セピオライト、活性アルミナ、ケイ酸アルミニウム、シリカゲル、アルミナゲル、活性白土、リン酸ジルコニウムやポリトリリン酸アンモニウム等の層状化合物、多孔性粘土鉱物といった無機粒子が挙げられ、これらの中から目的に応じて選択することができる。中でも多孔質シリカは安価に調達可能であり好ましい。 Among them, the gas adsorbent of the present invention preferably contains a chemical adsorbent that adsorbs an aldehyde by a chemical reaction. Since the gas adsorbent of the present invention contains a chemical adsorbent that adsorbs aldehydes by a chemical reaction, the adsorption capacity of formaldehyde can be improved and desorption after gas adsorption is small, so that it can be used as an air purifier. When used, it is preferable because it can suppress a decrease in the space removal capacity (CADR) of formaldehyde. Examples of the chemical adsorbent include hydrazide compounds such as adipic acid dihydrazide, dodecanedioic acid dihydrazide, and succinate dihydrazide, which are primary to tertiary amine compounds, p-aminobenzenesulfonic acid, ethylene urea condensate, and tris ( Hydroxylmethyl) aminomethane and the like. In particular, adipic acid dihydrazide is preferable in terms of adsorption performance of aldehydes. Further, as the structure of the chemisorbent, it is more preferable to support the chemisorbent on the surface of a porous body (a carrier made of a porous substance) because the contact efficiency with the aldehyde gas can be improved. Porous bodies include activated carbon, porous silica, zeolite, sepiolite, active alumina, aluminum silicate, silica gel, alumina gel, activated clay, layered compounds such as zirconium phosphate and ammonium polytriphosphate, and inorganics such as porous clay minerals. Particles can be mentioned and can be selected from these according to the purpose. Among them, porous silica is preferable because it can be procured at low cost.
　化学吸着剤を含む場合、ガス吸着剤における化学吸着剤の含有量は、４０質量％以上であることが好ましく、５０質量％以上であることがより好ましく、６０質量％以上であることがさらに好ましい。また、上限は、８０質量％以下であることが好ましく、７５質量％以下であることがより好ましく、７０質量％以下であることがさらに好ましい。 When the chemical adsorbent is contained, the content of the chemical adsorbent in the gas adsorbent is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more. .. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less.
　本発明のガス吸着剤は、トルエンの飽和吸着後のトルエンの脱離率が２５％以下であることが好ましい。そして、トルエンの飽和吸着後のトルエンの脱離率が２５％以下である本発明のガス吸着剤は、このガス吸着剤を用いたエアフィルターにおいて、一旦、エアフィルターに吸着されたトルエンなどの臭気成分のエアフィルターからの脱離を抑制することができる。 The gas adsorbent of the present invention preferably has a toluene desorption rate of 25% or less after saturated adsorption of toluene. The gas adsorbent of the present invention having a toluene desorption rate of 25% or less after saturated adsorption of toluene has an odor such as toluene once adsorbed on the air filter in an air filter using this gas adsorbent. Desorption of components from the air filter can be suppressed.
　ここで、トルエンの飽和吸着とは、後述する実施例の項の「（１）トルエンの飽和吸着量（ｇ／ｍ２）」に記載のとおり、ガス吸着剤にトルエンが吸着された状態を示す。 Here, the saturated adsorption of toluene means a state in which toluene is adsorbed on the gas adsorbent as described in "(1) Saturated adsorption amount of toluene (g / m 2 )" in the section of Examples described later. ..
　また、トルエンの脱離率とは、後述する実施例の項の「（２）トルエンの脱離率（％）」に記載の方法にて測定されるものである。 Further, the toluene desorption rate is measured by the method described in "(2) Toluene desorption rate (%)" in the section of Examples described later.
　トルエンの飽和吸着状態における吸着量は、ガス吸着剤をエアフィルターとして使用した際のタバコ臭気の除去性能など、有機ガスに対する上述した物理吸着特性の寿命に関するものである。トルエンの飽和吸着量は、後述する実施例の項の「（１）トルエンの飽和吸着量（ｇ／ｍ２）」に記載の測定方法にて１０ｇ／ｍ２以上であることが好ましく。より好ましくは２０ｇ／ｍ２以上である。 The amount of toluene adsorbed in the saturated adsorption state relates to the life of the above-mentioned physical adsorption characteristics for organic gas, such as the ability to remove tobacco odor when a gas adsorbent is used as an air filter. The saturated adsorption amount of toluene is preferably 10 g / m 2 or more by the measuring method described in "(1) Saturated adsorption amount of toluene (g / m 2 )" in the section of Examples described later. More preferably, it is 20 g / m 2 or more.
　高いトルエン飽和吸着量を有し、かつ二次発臭と称する臭気の再放出を抑えるためには、トルエン吸着後の脱離量を低減することが必要である。これは、ガス吸着剤をエアフィルターとして用いた際の二次発臭が、使用中に吸着されたガス成分の脱離に強く起因していると考えられるためである。 It is necessary to reduce the amount of desorption after toluene adsorption in order to have a high amount of toluene saturated adsorption and to suppress the re-emission of odor called secondary odor. This is because it is considered that the secondary odor when the gas adsorbent is used as an air filter is strongly caused by the desorption of the gas component adsorbed during use.
　本発明におけるガス吸着剤は、シート状に形成されて用いられることが好ましい。すなわち、本発明のガス吸着剤はガス吸着シートに好適に用いられる。ここでいうガス吸着剤がシート状に形成されているとは、ガス吸着剤粒子を繊維間に分散させたり、積層した不織布間に挟持させることを示し、繊維シートの集塵性能を維持したまま、脱臭性能を付加することができる。具体的な製造方法としては、例えばガス吸着剤と熱接着性繊維を混合分散させたものを捕集ネット上の基材不織布の上に吸引積層した後、加熱炉で融着一体化させ、加熱炉出口でカバー不織布を貼り合わせる、所謂エアレイド法を採用することが挙げられる。それ以外の方法として、例えば基材不織布上にガス吸着剤粒子と粉末状の熱接着樹脂粒子を定量均一散布し、ヒーターで熱接着樹脂粒子を加熱溶融した後、カバー不織布を積層圧着することにより一体化する方法や、基材不織布上に加熱溶融樹脂をスプレーしながらガス吸着剤粒子を散布した後、カバー不織布を積層圧着することにより一体化する方法などが挙げられるが、これに限定されるものでは無い。 The gas adsorbent in the present invention is preferably used after being formed in a sheet shape. That is, the gas adsorbent of the present invention is suitably used for a gas adsorbent sheet. The fact that the gas adsorbent is formed in the form of a sheet means that the gas adsorbent particles are dispersed between the fibers or sandwiched between the laminated non-woven fabrics, and the dust collecting performance of the fiber sheet is maintained. , Deodorizing performance can be added. As a specific manufacturing method, for example, a gas adsorbent and a heat-adhesive fiber mixed and dispersed are suction-laminated on a base material non-woven fabric on a collection net, then fused and integrated in a heating furnace and heated. It is possible to adopt the so-called air-laid method in which the cover non-woven fabric is bonded at the furnace outlet. As another method, for example, gas adsorbent particles and powdered heat-adhesive resin particles are quantitatively and uniformly sprayed on the base non-woven fabric, the heat-adhesive resin particles are heated and melted by a heater, and then the cover non-woven fabric is laminated and pressure-bonded. Examples include, but are limited to, a method of integrating by spraying gas adsorbent particles on the base non-woven fabric while spraying a heated molten resin, and then laminating and pressure-bonding the cover non-woven fabric. It's not a thing.
　本発明におけるガス吸着剤がシート状に形成される際のガス吸着剤の目付は、１５～４００ｇ／ｍ２の範囲とすることが好ましく、３０～３００ｇ／ｍ２の範囲とすることにより、ガス吸着容量が高く、かつ得られたシート状濾材をエアフィルターに加工する際のプリーツ（折り曲げ）加工性に優れるためより好ましい。ガス吸着剤の形状としては特に限定されず、球状、板状、多角形状、不定形状等が挙げられ、破砕状態のものや成型されたものなど公知のものから任意に選定可能である。ガス吸着剤の大きさとしては、特に指定されるものではないが、平均粒子径５０～４００μｍの粒状のものを用いることが、シート状に形成した後の濾材をエアフィルターに加工する際のプリーツ加工性に優れるため好ましい。 When the gas adsorbent in the present invention is formed in the form of a sheet, the texture of the gas adsorbent is preferably in the range of 15 to 400 g / m 2 , and by setting it in the range of 30 to 300 g / m 2 , the gas It is more preferable because it has a high adsorption capacity and is excellent in pleating (bending) workability when processing the obtained sheet-shaped filter medium into an air filter. The shape of the gas adsorbent is not particularly limited, and examples thereof include a spherical shape, a plate shape, a polygonal shape, an indefinite shape, and the like, and any known shape such as a crushed one or a molded one can be arbitrarily selected. The size of the gas adsorbent is not particularly specified, but it is recommended to use a granular gas adsorbent having an average particle diameter of 50 to 400 μm when processing the filter medium after forming it into a sheet into an air filter. It is preferable because it has excellent workability.
　なお、ここで言う平均粒子径とは、ＪＩＳ－Ｚ－８８１５（１９９４）によって粒子径分布を測定し、粒状ガス吸着剤の総質量の５０質量％が通過するふるい目の大きさに相当する粒子径である。 The average particle size referred to here is a particle corresponding to the size of a sieve through which 50% by mass of the total mass of the granular gas adsorbent is measured by measuring the particle size distribution by JIS-Z-8815 (1994). The diameter.
　本発明におけるガス吸着剤は濾材に好適に用いられる。そして、上記の濾材は、２層以上の不織布と本発明のガス吸着剤とを有し、本発明のガス吸着剤は２層以上の不織布により形成される１つ以上の層間の少なくとも１つに保持される。なお、上記の濾材は、エアフィルターに好適に用いることができる。ここで、不織布の形態は特に限定されず、ケミカルボンド不織布、湿式抄紙不織布、スパンボンド不織布、メルトブロー不織布、スパンレース不織布およびエアレイド不織布等が挙げられる。 The gas adsorbent in the present invention is preferably used for a filter medium. The filter medium has two or more layers of a non-woven fabric and the gas adsorbent of the present invention, and the gas adsorbent of the present invention is applied to at least one of one or more layers formed by the two or more layers of the non-woven fabric. Be retained. The above filter medium can be suitably used for an air filter. Here, the form of the non-woven fabric is not particularly limited, and examples thereof include chemical-bonded non-woven fabrics, wet papermaking non-woven fabrics, spunbonded non-woven fabrics, melt-blown non-woven fabrics, spunlaced non-woven fabrics, and air-laid non-woven fabrics.
　上記の濾材が備える不織布は、エレクトレット不織布であることが好ましい。エレクトレット不織布であることで、上記の濾材は空気中の粉塵をより高い効率で捕集できるため好ましい。ここで、エレクトレット不織布は、不織布にエレクトレット加工を施すことで得ることができる。そして、エレクトレット加工とは、不織布に電荷を付与し、その静電気力によって空気中の粉塵を捕集する特性を不織布に付与する加工である。電荷の付与方法（すなわち、エレクトレット加工）としては、特に指定されるものではなく、不織布に対し、コロナ放電法、ハイドロチャージ法、摩擦帯電法といった方法を採用することができ、中でもより高い電荷量が得られるとの観点から純水サクション方式によるハイドロチャージ法を用いることが好ましい。 The non-woven fabric provided in the above filter medium is preferably an electret non-woven fabric. The electret non-woven fabric is preferable because the above-mentioned filter medium can collect dust in the air with higher efficiency. Here, the electret non-woven fabric can be obtained by subjecting the non-woven fabric to electret processing. The electret processing is a process of imparting an electric charge to the non-woven fabric and imparting the property of collecting dust in the air to the non-woven fabric by the electrostatic force. The method of applying electric charge (that is, electret processing) is not particularly specified, and a method such as a corona discharge method, a hydrocharge method, or a triboelectric charge method can be adopted for the non-woven fabric, and a higher charge amount among them. From the viewpoint of obtaining the above, it is preferable to use the hydrocharge method by the pure water suction method.
　本発明のガス吸着剤を不織布に担持させる方法としては、前記したとおり複数の方法がある。例えば、粒子状のガス吸着剤を、このガス吸着剤と同等の粒子サイズを有するポリエチレン樹脂などからなる熱により接着する接着パウダーと均一に混合したもの（以下、ガス複合吸着剤ということがある）を不織布の一方の平面上に均一に散布し、加熱して接着パウダーを溶融させることで、接着パウダーに流動性が生じガス吸着剤粒子同士および／またはガス吸着剤とカバー層が連結した状態で、別の不織布をガス吸着剤散布面に重ね積層体を得て、この積層体を所定の間隔に設定されたニップロール間を通すことでラミネートする方法などが好ましく利用される。ここでのガス吸着剤の散布量は１５～４００ｇ／ｍ２の範囲とすることが好ましい。 As described above, there are a plurality of methods for supporting the gas adsorbent of the present invention on the non-woven fabric. For example, a particulate gas adsorbent is uniformly mixed with an adhesive powder that adheres by heat, such as a polyethylene resin having a particle size equivalent to that of the gas adsorbent (hereinafter, may be referred to as a gas composite adsorbent). Is uniformly sprayed on one flat surface of the non-woven fabric and heated to melt the adhesive powder, so that the adhesive powder becomes fluid and the gas adsorbent particles and / or the gas adsorbent and the cover layer are connected to each other. , A method in which another non-woven fabric is laminated on the gas adsorbent spraying surface to obtain a laminated body, and the laminated body is passed between nip rolls set at predetermined intervals to be laminated is preferably used. The amount of the gas adsorbent sprayed here is preferably in the range of 15 to 400 g / m 2 .
　上記不織布の厚みとしては、一定の強度を有し、かつプリーツ折り加工をした際に一定容積に収容できる面積を増やす観点から、０．０８～０．６０ｍｍとすることが好ましく、その下限は０．１５ｍｍ以上とすることがより好ましく、その上限は０．５０ｍｍ以下とすることがより好ましい。なお、上記の濾材は、２層以上の不織布を有しているが、これらの不織布の厚さは同じでも、異なっていてもよい。 The thickness of the non-woven fabric is preferably 0.08 to 0.60 mm from the viewpoint of having a certain strength and increasing the area that can be accommodated in a certain volume when pleated, and the lower limit thereof is 0. It is more preferably .15 mm or more, and the upper limit thereof is more preferably 0.50 mm or less. The above-mentioned filter medium has two or more layers of non-woven fabric, and the thickness of these non-woven fabrics may be the same or different.
　上記の不織布に使用する繊維としては、天然繊維、合成繊維またはガラス繊維もしくは金属繊維等の無機繊維が使用でき、中でも溶融紡糸が可能な熱可塑性樹脂の合成繊維が好ましい。合成繊維を形成する熱可塑性樹脂の例としては、ポリエステル、ポリアミド、ポリオレフィン、アクリル、ビニロン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ乳酸等を挙げることができ、用途等に応じて選択できる。また、複数種を組み合わせて使用してもよい。エレクトレット処理による高いエレクトレット性能の付与の観点からポリプロピレン、ポリエチレン、ポリスチレン等のポリオレフィン系樹脂、ポリエチレンテレフタレート等の芳香族ポリエステル系樹脂またはポリカーボネート樹脂等の高い電気抵抗率を有する材料が好ましい。 As the fiber used for the above-mentioned non-woven fabric, natural fiber, synthetic fiber or inorganic fiber such as glass fiber or metal fiber can be used, and among them, synthetic fiber of thermoplastic resin capable of melt spinning is preferable. Examples of the thermoplastic resin forming the synthetic fiber include polyester, polyamide, polyolefin, acrylic, vinylon, polystyrene, polyvinyl chloride, polyvinylidene chloride, polylactic acid, and the like, which can be selected according to the intended use. Further, a plurality of types may be used in combination. From the viewpoint of imparting high electlet performance by the electlet treatment, a material having a high electric resistance such as a polyolefin resin such as polypropylene, polyethylene and polystyrene, an aromatic polyester resin such as polyethylene terephthalate or a polycarbonate resin is preferable.
　また、本発明のガス吸着剤を備える濾材は、エアフィルターに好適に用いることができる。そして、上記のエアフィルターは、プリーツ形状の上記の濾材の四方と外枠とが固定されてなる。ここで、上記の濾材はプリーツ加工された状態で山谷を有する立体形状を形成している。そして、プリーツ加工とは、上記した濾材を一定方向に所定の折高さで山谷形状に折り込んだものであり、折り込みの方法としては、レシプロ式、ロータリー式などの方法を用いることができる。プリーツ加工をすることによってエアフィルターとして一定容積の中により多くの面積の濾材を収載したエアフィルターを得ることができる。 Further, the filter medium provided with the gas adsorbent of the present invention can be suitably used for an air filter. The air filter is formed by fixing the four sides of the pleated filter medium and the outer frame. Here, the above-mentioned filter medium forms a three-dimensional shape having peaks and valleys in a pleated state. The pleating process is a process in which the above-mentioned filter medium is folded into a mountain valley shape at a predetermined folding height in a certain direction, and a method such as a reciprocating type or a rotary type can be used as the folding method. By pleating, it is possible to obtain an air filter in which a larger area of filter media is placed in a fixed volume as an air filter.
　また、プリーツ加工によって形成された複数の山谷形状同士の間隔を一定に保持するために、隣接する山間に生じるスペースに、セパレーターを設けることができる。溶融樹脂をプリーツの山の稜線に沿うよう線状に塗布し、隣接する樹脂同士を接着固定するビード接着など、公知の方法を用いて、複数の山谷形状にプリーツ加工された濾材の間隔を一定に保持させてもよい。 Further, in order to keep the distance between the plurality of mountain valley shapes formed by the pleating process constant, a separator can be provided in the space generated between the adjacent mountains. Using a known method such as bead bonding in which molten resin is applied linearly along the ridgeline of the pleated peaks and adjacent resins are bonded and fixed to each other, the intervals between the filter media pleated into a plurality of peaks and valleys are fixed. May be retained by.
　また、本発明におけるエアフィルターは、所定のサイズに成形することを目的に、上記プリーツ加工した濾材の外周に外枠を取り付ける。取り付け方法としては特に指定されるものではないが、プリーツ加工された濾材の外周４辺に、ポリオレフィン系ホットメルトなどの接着剤を塗布した平板状の不織布を貼り付け、直方体のエアフィルターを形成する方法が挙げられる。 Further, in the air filter of the present invention, an outer frame is attached to the outer circumference of the pleated filter medium for the purpose of molding into a predetermined size. Although the mounting method is not particularly specified, a flat non-woven fabric coated with an adhesive such as a polyolefin hot melt is pasted on the four outer peripheral sides of the pleated filter medium to form a rectangular parallelepiped air filter. The method can be mentioned.
　以下、実施例によって本発明の作用効果をより具体的に示すが、本発明は下記実施例のみに限定されるものではない。 Hereinafter, the effects of the present invention will be shown more specifically by Examples, but the present invention is not limited to the following Examples.
　［ガス吸着剤を用いた濾材の製造方法］
　ガス吸着剤とポリエチレン系接着パウダー（ＡｂｉｆｏｒＡＧ社製　Ａｂｉｆｏｒ１２００）（以下、接着パウダーとする）を、ガス吸着剤：接着パウダー＝２：１（質量比）の割合でブレンドし、それをポリエステル繊維からなるスパンボンド不織布（東レ株式会社製　アクスターＨ２０７０－７Ｓ）上に６０ｇ／ｍ２（うちガス吸着剤が４０ｇ／ｍ２）となるように均一に散布した。その後、加熱炉内で１１０℃～１３０℃に加熱することにより接着パウダーを溶融させ、その散布面にエレクトレットメルトブロー不織布（目付３０ｇ／ｍ２）を積層後、ニップロールによって加圧し、所定の厚みのシート状の濾材を得た。 [Manufacturing method of filter media using gas adsorbent]
A gas adsorbent and a polyethylene-based adhesive powder (Abifor 1200 manufactured by Abifor AG) (hereinafter referred to as an adhesive powder) are blended at a ratio of gas adsorbent: adhesive powder = 2: 1 (mass ratio), and the mixture is composed of polyester fibers. It was uniformly sprayed on a spunbonded non-woven fabric (Axter H2070-7S manufactured by Toray Co., Ltd.) so as to have a gas adsorbent of 60 g / m 2 (of which the gas adsorbent was 40 g / m 2 ). Then, the adhesive powder is melted by heating to 110 ° C. to 130 ° C. in a heating furnace, an electret melt blown non-woven fabric (with a basis weight of 30 g / m 2 ) is laminated on the spray surface, and then pressed by a nip roll to form a sheet having a predetermined thickness. A filter medium was obtained.
　［測定方法］
（１）トルエンの飽和吸着量（ｇ／ｍ２）
　上記製造方法で得られたガス吸着剤を用いたシート状濾材を１０ｃｍ×１０ｃｍの四角形に採取し、それを８０℃に加熱した乾燥機内に入れ、２時間乾燥処理し、取り出した濾材の質量（ｇ）を電子天秤で測定した。得られた測定値をｍ１（ｇ）とした。次に、湿度を５０％ＲＨに管理した１０Ｌのデシケーター内にトルエンを飽和させ、そこに質量測定した後の濾材を投入し、２４時間放置した。そして、上記のデシケーター内から取り出した後の濾材の質量（ｇ）を電子天秤で測定した。得られた測定値をｍ２（ｇ）とした。次に、下記計算式より、濾材の単位面積当たりのトルエン吸着容量を算出し、ガス吸着剤の４０ｇ／ｍ２あたりのトルエンの飽和吸着量を求めた。
　　トルエン吸着容量（ｇ／ｍ２）＝（ｍ２－ｍ１）／（０．１＊０．１） [Measuring method]
(1) Saturated adsorption amount of toluene (g / m 2 )
A sheet-shaped filter medium using the gas adsorbent obtained by the above manufacturing method was collected in a square of 10 cm × 10 cm, placed in a dryer heated to 80 ° C., dried for 2 hours, and the mass of the removed filter medium ( g) was measured with an electronic balance. The obtained measured value was defined as m1 (g). Next, toluene was saturated in a 10 L desiccator whose humidity was controlled to 50% RH, and the filter medium after mass measurement was put therein and left for 24 hours. Then, the mass (g) of the filter medium after being taken out from the above desiccator was measured with an electronic balance. The obtained measured value was defined as m2 (g). Next, the toluene adsorption capacity per unit area of the filter medium was calculated from the following formula, and the saturated adsorption amount of toluene per 40 g / m 2 of the gas adsorbent was determined.
Toluene adsorption capacity (g / m 2 ) = (m2-m1) / (0.1 * 0.1)
（２）トルエンの脱離率（％）
　上記（１）に記載のトルエンの飽和吸着量を測定した後の濾材から直径６ｃｍの円形の濾材サンプル（面積２８．３ｃｍ２）を採取した。通風直径４ｃｍ、および胴部長さ１５ｃｍからなる円筒形風洞を２つ用意し、それぞれを濾材サンプルの一方の面側と他方の面側とに取り付けた。次に、濾材サンプルの一方の面側から他方の面側の方向に、温度が２０℃、湿度が５０％ＲＨの空気を風速０．０６ｍ／秒で通過させた。濾材サンプルに空気を通過させた２０秒後から、濾材サンプルの下流側（濾材サンプルの他方の面側）の空気のトルエン濃度（ｐｐｍ）を、赤外吸光式ガス濃度計（日本サーモ株式会社製　ＭＩＲＡＮ ＳａｐｐｈｌＲｅ）を用いて２秒間隔で５分間測定し、検出された空気中のトルエンの濃度よりトルエンの積算脱離量を測定し、得られた測定結果から単位面積（１ｍ２）あたりのトルエンの積算脱離量（ｇ／ｍ２）を計算した。そして、このトルエンの積算脱離量（ｇ／ｍ２）を上記（１）記載の方法で測定したトルエン飽和吸着量（ｇ／ｍ２）で除し、さらに１００を乗ずることで、ガス吸着剤の４０ｇ／ｍ２あたりのトルエンの脱離率（％）を算出した。 (2) Toluene desorption rate (%)
A circular filter medium sample (area 28.3 cm 2 ) having a diameter of 6 cm was collected from the filter medium after measuring the saturated adsorption amount of toluene described in (1) above. Two cylindrical wind tunnels having a ventilation diameter of 4 cm and a body length of 15 cm were prepared, and each was attached to one side and the other side of the filter medium sample. Next, air having a temperature of 20 ° C. and a humidity of 50% RH was passed from one surface side of the filter medium sample to the other surface side at a wind speed of 0.06 m / sec. From 20 seconds after passing air through the filter medium sample, the toluene concentration (ppm) of the air on the downstream side of the filter medium sample (the other surface side of the filter medium sample) is measured by an infrared absorption type gas densitometer (manufactured by Nippon Thermo Co., Ltd.). MIRAN SapphlRe) was used to measure for 5 minutes at 2-second intervals, and the integrated desorption amount of toluene was measured from the detected concentration of toluene in the air. From the obtained measurement results, toluene per unit area (1 m 2 ) was measured. The cumulative desorption amount (g / m 2 ) of was calculated. Then, the integrated amount of released toluene (g / m 2) divided by (1) toluene saturated adsorption amount was measured by the method described (g / m 2), by further multiplying the 100, gas adsorbent The desorption rate (%) of toluene per 40 g / m 2 of the above was calculated.
（３）ホルムアルデヒドの空間浄化能力（ＣＡＤＲ）（ｍ３／ｈｒ）
　上記［ガス吸着剤を用いた濾材の製造方法］で得られた濾材を、巾２８９ｍｍ、長さ７．８ｍ分作製し、レシプロプリーツ加工機（ホップテック株式会社製　Ｗ６５０）を用いて濾材の長さ方向に対し折高さ５８ｍｍ＊６６山分プリーツ加工した。その後、その濾材を一度展開し、濾材表裏の各面上に、ホットメルトアプリケーター（ＩＴＷダイナテック株式会社製　Ｄｙｎａｍｅｌｔ）を用いて１８０℃に加熱し溶融させたポリオレフィン系樹脂（日立化成ポリマー株式会社製　ハイボン９５００）を、圧空ノズルを用いて太さ３ｍｍ、濾材巾方向に対し５ｃｍ間隔で計６本連続で塗布した後、再度プリーツ加工の折り目に合わせて折り畳み、隣接するプリーツ山同士の間隔が５．６ｍｍとなるよう、線状のホットメルト樹脂同士を接着固定させ、略直方体のプリーツ形状の濾材を得た。その濾材に対し、ロールコーター（株式会社エピック製　Ｒ２）にて２００℃で加熱、溶融させたポリオレフィン系接着剤（日立化成ポリマー株式会社製　ハイボンＹＨ４５０－１）を、目付２６０ｇ／ｍ２、厚み１ｍｍのポリエステルサーマルボンド不織布を巾６０ｍｍにカットした外枠の片側全面に塗布後、この外枠をプリーツ形状の濾材の四方に貼り付け、間口サイズとして縦３７２ｍｍ、横２９１ｍｍで、高さ６０ｍｍのエアフィルターを得た。上記エアフィルターを市販の空気清浄機（定格風量４５０ｍ３／時）に搭載後、３０ｍ３の試験室内に設置し、「ＧＢ／Ｔ　１８００１－２０１５　Ａｉｒ　ｃｌｅａｎｅｒ」に準拠した方法にて、ホルムアルデヒドのＣＡＤＲ（ｍ３／ｈｒ）を測定した。 (3) Formaldehyde spatial purification capacity (CADR) (m 3 / hr)
The filter medium obtained in the above [Method for manufacturing a filter medium using a gas adsorbent] was prepared for a width of 289 mm and a length of 7.8 m, and the length of the filter medium was manufactured using a reciprocating pleating machine (W650 manufactured by Hoptech Co., Ltd.). Folded height 58 mm * 66 pleats were processed in the vertical direction. After that, the filter medium was once developed, and a polyolefin resin (manufactured by Hitachi Chemical Polymer Co., Ltd.) was melted by heating to 180 ° C. using a hot melt applicator (Dynamelt manufactured by ITW Dynatec Co., Ltd.) on the front and back surfaces of the filter medium. Hybon 9500) was applied in succession using a compression nozzle to a thickness of 3 mm and at intervals of 5 cm in the filter medium width direction, and then folded again according to the creases of the pleating process, and the distance between adjacent pleats was 5 The linear hot-melt resins were adhered and fixed to each other so as to have a thickness of 0.6 mm, and a substantially rectangular pleated filter medium was obtained. A polyolefin adhesive (Hybon YH450-1 manufactured by Hitachi Kasei Polymer Co., Ltd.) heated and melted at 200 ° C. with a roll coater (R2 manufactured by Epic Co., Ltd.) was applied to the filter medium with a grain size of 260 g / m 2 and a thickness of 1 mm. After applying the polyester thermal bond non-woven fabric of No. 1 to the entire surface of one side of the outer frame cut to a width of 60 mm, this outer frame is attached to all sides of the pleated filter medium, and the frontage size is 372 mm in length, 291 mm in width, and 60 mm in height. Got After mounting the above air filter on a commercially available air purifier (rated air volume 450 m 3 / hour), install it in a test room of 30 m 3 and use a method compliant with "GB / T 18001-2015 Air cleaner" to CADR formaldehyde. (M 3 / hr) was measured.
（４）ホルムアルデヒド累積浄化量（ＣＣＭ）（ｍｇ）
　上記（３）記載のＣＡＤＲ（ｍ３／ｈｒ）を測定後、「ＧＢ／Ｔ　１８００１－２０１５　Ａｉｒ　ｃｌｅａｎｅｒ」に準拠した方法にて、ホルムアルデヒドガス３００ｍｇを空気清浄の運転によってエアフィルターに吸着させた後、上記（３）と同じ測定方法にてホルムアルデヒドのＣＡＤＲ（ｍ３／ｈｒ）を測定した。これをホルムアルデヒドのＣＡＤＲ（ｍ３／ｈｒ）が上記（３）で測定したＣＡＤＲ（ｍ３／ｈｒ）の半分に低下するまでくり返し、ＣＡＤＲ（ｍ３／ｈｒ）が半分に到達した時点でのホルムアルデヒドガスの総吸着量を算出した。 (4) Cumulative purification of formaldehyde (CCM) (mg)
After measuring the CADR (m 3 / hr) described in (3) above, 300 mg of formaldehyde gas is adsorbed on the air filter by an air purifying operation by a method based on "GB / T 18001-2015 Air cleaner". , CADR (m 3 / hr) of formaldehyde was measured by the same measuring method as in (3) above. This repeated until the formaldehyde CADR (m 3 / hr) is reduced to half the above (3) CADR measured in (m 3 / hr), formaldehyde at the time the CADR (m 3 / hr) reaches to half The total amount of gas adsorbed was calculated.
（５）二次発臭（点）および快不快度（点）
　上記（３）と同様の方法で得られたエアフィルターを市販の空気清浄機（定格風量４５０ｍ３／時）に搭載した。次に、この空気清浄機を容積１ｍ３の透明アクリル製の試験室内に設置し、その試験室内でタバコ（メビウス１０ｍｇ）５本を燃焼させた後、空気清浄機を稼働させ、燃焼煙をエアフィルターに３０分間捕集させた。この作業を１０回繰り返し、計５０本分のタバコ燃焼煙を捕集させた。
　上記タバコ燃焼煙捕集後の空気清浄機を、容積３０ｍ３の試験室内で稼働せずに２４時間放置し、その後空気清浄機を稼働させ、排出される空気の臭気強度、および快不快度を、表３および表４に示す判定基準で、５人のパネラーが採点し、その平均値を求めた。 (5) Secondary odor (point) and degree of comfort (point)
The air filter obtained by the same method as in (3) above was mounted on a commercially available air purifier (rated air volume 450 m 3 / hour). Then, the air purifier was installed in a test chamber made of clear acrylic volume 1 m 3, after burn tobacco (Moebius 10 mg) 5 present in the test chamber, operate the air cleaner, the air combustion fumes The filter was allowed to collect for 30 minutes. This work was repeated 10 times to collect a total of 50 cigarette smokes.
The air purifier after collecting the cigarette combustion smoke was left for 24 hours without operating in a test room having a volume of 30 m 3 , and then the air purifier was operated to check the odor intensity and the degree of comfort and discomfort of the discharged air. , 5 panelists scored according to the criteria shown in Tables 3 and 4, and the average value was calculated.
［実施例１］
　ガス吸着剤として粒状活性炭（フタムラ化学株式会社製　ＣＮ３６０Ｓ）（ガス吸着剤の構成材料１）のみを用いた。上記のガス吸着剤を有する濾材を上記の［ガス吸着剤を用いた濾材の製造方法］に記載の方法で製造した。この濾材の厚みは０．９ｍｍであった。
　また、得られた濾材にプリーツ加工を施し、さらにプリーツ形状の濾材の四方に外枠を取り付けることでエアフィルターを得た。
　実施例１のガス吸着剤で用いた粒状活性炭、実施例１のガス吸着剤および実施例１のガス吸着剤を用いたエアフィルターについて表１にまとめた。 [Example 1]
Only granular activated carbon (CN360S manufactured by Futamura Chemical Co., Ltd.) (constituent material 1 of the gas adsorbent) was used as the gas adsorbent. A filter medium having the above gas adsorbent was produced by the method described in the above [Method for producing a filter medium using a gas adsorbent]. The thickness of this filter medium was 0.9 mm.
Further, the obtained filter medium was pleated, and outer frames were attached to the four sides of the pleated filter medium to obtain an air filter.
Table 1 summarizes the granular activated carbon used in the gas adsorbent of Example 1, the gas adsorbent of Example 1, and the air filter using the gas adsorbent of Example 1.
［実施例２］
　ガス吸着剤として粒状活性炭（株式会社クラレ製　クラレコール（登録商標）ＧＷ３０／６０Ｄ）（ガス吸着剤の構成材料１）のみを用いた。上記のガス吸着剤を有する濾材を上記の［ガス吸着剤を用いた濾材の製造方法］に記載の方法で製造した。この濾材の厚みは０．９ｍｍであった。
　また、得られた濾材にプリーツ加工を施し、さらにプリーツ形状の濾材の四方に外枠を取り付けることでエアフィルターを得た。
　実施例２のガス吸着剤で用いた粒状活性炭、実施例２のガス吸着剤および実施例２のガス吸着剤を用いたエアフィルターについて表１にまとめた。 [Example 2]
Only granular activated carbon (Kuraray Coal (registered trademark) GW30 / 60D) (constituent material 1 of the gas adsorbent) was used as the gas adsorbent. A filter medium having the above gas adsorbent was produced by the method described in the above [Method for producing a filter medium using a gas adsorbent]. The thickness of this filter medium was 0.9 mm.
Further, the obtained filter medium was pleated, and outer frames were attached to the four sides of the pleated filter medium to obtain an air filter.
Table 1 summarizes the granular activated carbon used in the gas adsorbent of Example 2, the gas adsorbent of Example 2, and the air filter using the gas adsorbent of Example 2.
［実施例３］
　実施例２のガス吸着剤に用いたものと同じ活性炭（ガス吸着剤の構成材料１）と、化学吸着剤としてアジピン酸ジヒドラジド（日本化成株式会社製）を添着させた多孔質シリカ粒子（富士シリシア化学株式会社製　ＳＹＬＹＳＩＡ　ＣＡＲＩＡＣＴ　Ｇ－６　細孔容積１．０ｃｃ／ｇ、比表面積５００ｍ２／ｇ、ＪＩＳ－Ｚ－８８１５（１９９４）に基づく測定方法による平均粒子径２００μｍ）（ガス吸着剤の構成材料２）とを、活性炭：化学吸着剤＝１：１（質量比）の割合で配合したガス吸着剤を用いた。なお、上記の化学吸着剤におけるアジピン酸ジヒドラジドの含有量は化学吸着剤全体に対し７質量％であった。上記のガス吸着剤を有する濾材を上記の［ガス吸着剤を用いた濾材の製造方法］に記載の方法で製造した。この濾材の厚みは１．０ｍｍであった。
　また、得られた濾材にプリーツ加工を施し、さらにプリーツ形状の濾材の四方に外枠を取り付けることでエアフィルターを得た。
　実施例３のガス吸着剤で用いた粒状活性炭、実施例３のガス吸着剤および実施例３のガス吸着剤を用いたエアフィルターについて表１にまとめた。 [Example 3]
Porous silica particles (Fuji Silicia) impregnated with the same activated carbon (constituent material 1 of the gas adsorbent) used for the gas adsorbent of Example 2 and dihydrazide adipate (manufactured by Nippon Kasei Co., Ltd.) as a chemical adsorbent. SYLYSIA CARIACT G-6 manufactured by Kagaku Co., Ltd. Pore volume 1.0 cc / g, specific surface area 500 m 2 / g, average particle size 200 μm by measurement method based on JIS-Z-8815 (1994)) (Constituent material of gas adsorbent A gas adsorbent containing 2) in a ratio of activated carbon: chemical adsorbent = 1: 1 (mass ratio) was used. The content of adipic acid dihydrazide in the above chemical adsorbent was 7% by mass with respect to the total amount of the chemical adsorbent. A filter medium having the above gas adsorbent was produced by the method described in the above [Method for producing a filter medium using a gas adsorbent]. The thickness of this filter medium was 1.0 mm.
Further, the obtained filter medium was pleated, and outer frames were attached to the four sides of the pleated filter medium to obtain an air filter.
Table 1 summarizes the granular activated carbon used in the gas adsorbent of Example 3, the gas adsorbent of Example 3, and the air filter using the gas adsorbent of Example 3.
［実施例４］
　実施例３のガス吸着剤に用いたものと同じ活性炭（ガス吸着剤の構成材料１）と、実施例３のガス吸着剤に用いたものと同じ化学吸着剤（ガス吸着剤の構成材料２）とを、活性炭：化学吸着剤＝３：１０（質量比）の割合で配合したガス吸着剤を用いた。なお、上記の化学吸着剤におけるアジピン酸ジヒドラジドの含有量は化学吸着剤全体に対し９質量％であった。上記のガス吸着剤を有する濾材を上記の［ガス吸着剤を用いた濾材の製造方法］に記載の方法で製造した。この濾材の厚みは１．０ｍｍであった。
　また、得られた濾材にプリーツ加工を施し、さらにプリーツ形状の濾材の四方に外枠を取り付けることでエアフィルターを得た。
　実施例４のガス吸着剤で用いた粒状活性炭、実施例４のガス吸着剤および実施例４のガス吸着剤を用いたエアフィルターについて表１にまとめた。 [Example 4]
The same activated carbon used for the gas adsorbent of Example 3 (constituent material 1 of the gas adsorbent) and the same chemical adsorbent used for the gas adsorbent of Example 3 (constituent material 2 of the gas adsorbent). A gas adsorbent prepared in a ratio of activated carbon: chemical adsorbent = 3:10 (mass ratio) was used. The content of adipic acid dihydrazide in the above chemical adsorbent was 9% by mass with respect to the total amount of the chemical adsorbent. A filter medium having the above gas adsorbent was produced by the method described in the above [Method for producing a filter medium using a gas adsorbent]. The thickness of this filter medium was 1.0 mm.
Further, the obtained filter medium was pleated, and outer frames were attached to the four sides of the pleated filter medium to obtain an air filter.
Table 1 summarizes the granular activated carbon used in the gas adsorbent of Example 4, the gas adsorbent of Example 4, and the air filter using the gas adsorbent of Example 4.
［比較例１］
　ガス吸着剤として粒状活性炭（大阪ガスケミカル株式会社製ＩＯＤＩＮ１１００ＵＷ）（ガス吸着剤の構成材料１）のみを用いた。上記のガス吸着剤を有する濾材を上記の［ガス吸着剤を用いた濾材の製造方法］に記載の方法で製造した。この濾材の厚みは０．８ｍｍであった。
　また、得られた濾材にプリーツ加工を施し、さらにプリーツ形状の濾材の四方に外枠を取り付けることでエアフィルターを得た。
　比較例１のガス吸着剤で用いた粒状活性炭、比較例１のガス吸着剤および比較例１のガス吸着剤を用いたエアフィルターについて表２にまとめた。 [Comparative Example 1]
Only granular activated carbon (IODIN1100UW manufactured by Osaka Gas Chemical Co., Ltd.) (constituent material 1 of the gas adsorbent) was used as the gas adsorbent. A filter medium having the above gas adsorbent was produced by the method described in the above [Method for producing a filter medium using a gas adsorbent]. The thickness of this filter medium was 0.8 mm.
Further, the obtained filter medium was pleated, and outer frames were attached to the four sides of the pleated filter medium to obtain an air filter.
Table 2 summarizes the granular activated carbon used in the gas adsorbent of Comparative Example 1, the gas adsorbent of Comparative Example 1, and the air filter using the gas adsorbent of Comparative Example 1.
［比較例２］
　ガス吸着剤として粒状活性炭（ヤシ殻原料／水蒸気賦活活性炭）（ガス吸着剤の構成材料１）のみを用いた。上記のガス吸着剤を有する濾材を上記の［ガス吸着剤を用いた濾材の製造方法］に記載の方法で製造した。この濾材の厚みは１．０ｍｍであった。
　また、得られた濾材にプリーツ加工を施し、さらにプリーツ形状の濾材の四方に外枠を取り付けることでエアフィルターを得た。
　比較例２のガス吸着剤で用いた粒状活性炭、比較例２のガス吸着剤および比較例２のガス吸着剤を用いたエアフィルターについて表２にまとめた。 [Comparative Example 2]
Only granular activated carbon (coconut shell raw material / steam-activated activated carbon) (constituent material 1 of the gas adsorbent) was used as the gas adsorbent. A filter medium having the above gas adsorbent was produced by the method described in the above [Method for producing a filter medium using a gas adsorbent]. The thickness of this filter medium was 1.0 mm.
Further, the obtained filter medium was pleated, and outer frames were attached to the four sides of the pleated filter medium to obtain an air filter.
Table 2 summarizes the granular activated carbon used in the gas adsorbent of Comparative Example 2, the gas adsorbent of Comparative Example 2, and the air filter using the gas adsorbent of Comparative Example 2.
［比較例３］
　ガス吸着剤として粒状活性炭（ヤシ殻原料／水蒸気賦活活性炭）（ガス吸着剤の構成材料１）のみを用いた。上記のガス吸着剤を有する濾材を上記の［ガス吸着剤を用いた濾材の製造方法］に記載の方法で製造した。この濾材の厚みは０．７ｍｍであった。
　また、得られた濾材にプリーツ加工を施し、さらにプリーツ形状の濾材の四方に外枠を取り付けることでエアフィルターを得た。
　比較例３のガス吸着剤で用いた粒状活性炭、比較例３のガス吸着剤および比較例３のガス吸着剤を用いたエアフィルターについて表２にまとめた。 [Comparative Example 3]
Only granular activated carbon (coconut shell raw material / steam activated carbon) (constituent material 1 of the gas adsorbent) was used as the gas adsorbent. A filter medium having the above gas adsorbent was produced by the method described in the above [Method for producing a filter medium using a gas adsorbent]. The thickness of this filter medium was 0.7 mm.
Further, the obtained filter medium was pleated, and outer frames were attached to the four sides of the pleated filter medium to obtain an air filter.
Table 2 summarizes the granular activated carbon used in the gas adsorbent of Comparative Example 3, the gas adsorbent of Comparative Example 3, and the air filter using the gas adsorbent of Comparative Example 3.
［比較例４］
　ガス吸着剤として粒状活性炭（ヤシ殻原料／塩酸賦活活性炭）（ガス吸着剤の構成材料１）のみを用いた。上記のガス吸着剤を有する濾材を上記の［ガス吸着剤を用いた濾材の製造方法］に記載の方法で製造した。この濾材の厚みは０．８ｍｍであった。
　また、得られた濾材にプリーツ加工を施し、さらにプリーツ形状の濾材の四方に外枠を取り付けることでエアフィルターを得た。
　比較例４のガス吸着剤で用いた粒状活性炭、比較例４のガス吸着剤および比較例４のガス吸着剤を用いたエアフィルターについて表２にまとめた。 [Comparative Example 4]
Only granular activated carbon (coconut shell raw material / hydrochloric acid activated carbon) (constituent material 1 of the gas adsorbent) was used as the gas adsorbent. A filter medium having the above gas adsorbent was produced by the method described in the above [Method for producing a filter medium using a gas adsorbent]. The thickness of this filter medium was 0.8 mm.
Further, the obtained filter medium was pleated, and outer frames were attached to the four sides of the pleated filter medium to obtain an air filter.
Table 2 summarizes the granular activated carbon used in the gas adsorbent of Comparative Example 4, the gas adsorbent of Comparative Example 4, and the air filter using the gas adsorbent of Comparative Example 4.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　実施例１、２では、トルエン飽和吸着が高く、かつトルエンの脱離率が少ないため、フィルターに加工し、空気清浄機に搭載した際のタバコ臭気吸着後の二次発臭の発生が少なく、使用者が不快感を感じ難いエアフィルターであった。さらに実施例３、４では、ホルムアルデヒドガスに対する空間浄化能力（ＣＡＤＲ）を長期間維持することができる。 In Examples 1 and 2, since toluene saturation adsorption is high and toluene desorption rate is low, secondary odor is less generated after tobacco odor adsorption when processed into a filter and mounted on an air purifier. It was an air filter that did not make the user feel uncomfortable. Further, in Examples 3 and 4, the space purification capacity (CADR) for formaldehyde gas can be maintained for a long period of time.
　比較例１、２は、トルエン飽和吸着量は高いが、トルエン吸着後のトルエン脱離率が高い。そのため、フィルターに加工し、空気清浄機に搭載した際のタバコ臭気吸着後のガス成分の再放出量が多くなり、二次発臭の強度が強く、不快度の高い臭気が感じられた。これは、ガス吸着剤として用いた活性炭の細孔構造が、二次発臭の低減に効果のあるＭＰ法で算出される０．４～２ｎｍの細孔で形成される細孔容積が少なく、２ｎｍを超える細孔から、吸着後のガスが再放出されやすいことが考えられる。 In Comparative Examples 1 and 2, the amount of saturated toluene adsorbed is high, but the rate of desorption of toluene after adsorption of toluene is high. Therefore, when the gas component was processed into a filter and mounted on an air purifier, the amount of re-emission of the gas component after adsorption of the tobacco odor increased, the intensity of the secondary odor was strong, and an odor with a high degree of discomfort was felt. This is because the pore structure of the activated carbon used as the gas adsorbent has a small pore volume formed by pores of 0.4 to 2 nm calculated by the MP method, which is effective in reducing secondary odor. It is considered that the gas after adsorption is likely to be re-released from the pores exceeding 2 nm.
　比較例３は、トルエン飽和吸着後のトルエン脱離率が高い。そのため、フィルターに加工し、空気清浄機に搭載した際のタバコ臭気吸着後のガス成分の再放出量が多くなり、二次発臭の強度が強く、不快度の高い臭気が感じられた。これは、ガス吸着剤として用いた活性炭の細孔容積が小さく、中でも二次発臭の低減に効果のあるＭＰ法で算出される０．４～２ｎｍの細孔で形成される細孔容積が少なく、タバコ臭気中の多様な臭気ガスに対し、吸着性能が低い高分子量のガスの再放出が発生しやすくなっていると考えられる。 Comparative Example 3 has a high toluene desorption rate after saturated adsorption of toluene. Therefore, when the gas component was processed into a filter and mounted on an air purifier, the amount of re-emission of the gas component after adsorption of the tobacco odor increased, the intensity of the secondary odor was strong, and an odor with a high degree of discomfort was felt. This is because the pore volume of the activated carbon used as the gas adsorbent is small, and the pore volume formed by the pores of 0.4 to 2 nm calculated by the MP method, which is effective in reducing the secondary odor, is particularly large. It is considered that the amount of high molecular weight gas having low adsorption performance is likely to be re-emitted with respect to various odorous gases in tobacco odor.
　比較例４は、トルエン飽和吸着量は高いが、トルエン吸着後のトルエン脱離率が著しく高い。そのため、フィルターに加工し、空気清浄機に搭載した際のタバコ臭気吸着後の二次発臭の強度が強く、不快度の高い臭気が感じられた。この原因は、以下のように推測する。活性炭には、ＭＰ法により算出される細孔径が０．４ｎｍ未満の細孔がほとんど存在しない。よって、活性炭に存在する細孔は、ＭＰ法により算出される細孔径が０．４～２ｎｍの細孔とＢＪＨ法により算出される細孔径が２ｎｍを超える細孔とに分けられる。そして、比較例４のガス吸着剤が有する活性炭はＭＰ法により算出される細孔径が０．４～２ｎｍの細孔の細孔容積が５１％であるため、上記の活性炭の全細孔の細孔容積のうちの４９％の細孔容積はＢＪＨ法により算出される細孔径が２ｎｍを超える細孔によるものであるといえる。すなわち、比較例４のガス吸着剤が有する活性炭にはＢＪＨ法により算出される細孔径が２ｎｍを超えるサイズの大きい細孔が多く存在しているといえ、これらのサイズの大きい細孔では１つの細孔当たりの空気との接触面積が大きくなるため、活性炭に吸着したタバコ臭気が再放出されやすいためと考える。 In Comparative Example 4, the amount of saturated toluene adsorbed is high, but the rate of desorption of toluene after adsorption of toluene is remarkably high. Therefore, when the product was processed into a filter and mounted on an air purifier, the intensity of the secondary odor after adsorption of the tobacco odor was strong, and a highly unpleasant odor was felt. The cause of this is presumed as follows. In activated carbon, there are almost no pores having a pore diameter of less than 0.4 nm calculated by the MP method. Therefore, the pores existing in the activated carbon are divided into pores having a pore diameter of 0.4 to 2 nm calculated by the MP method and pores having a pore diameter of more than 2 nm calculated by the BJH method. Since the activated carbon contained in the gas adsorbent of Comparative Example 4 has a pore volume of 51% of pores having a pore diameter of 0.4 to 2 nm calculated by the MP method, all the pores of the above activated carbon are fine. It can be said that 49% of the pore volume is due to the pores having a pore diameter of more than 2 nm calculated by the BJH method. That is, it can be said that the activated carbon contained in the gas adsorbent of Comparative Example 4 has many large pores having a pore diameter of more than 2 nm calculated by the BJH method, and one of these large pores has one. It is considered that the tobacco odor adsorbed on the activated carbon is easily re-emitted because the contact area with air per pore becomes large.
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は、２０１９年３月２９日出願の日本特許出願（特願２０１９－０６６８０１）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on March 29, 2019 (Japanese Patent Application No. 2019-066801), the contents of which are incorporated herein by reference.
　本発明によるガス吸着剤は、主に家庭用空気清浄機に搭載され、室内空気を清浄化するためのエアフィルターおよび濾材に使用される。 The gas adsorbent according to the present invention is mainly mounted on a household air purifier and is used for an air filter and a filter medium for purifying indoor air.

Claims (7)

  1. 　活性炭を含むガス吸着剤であって、
    　前記活性炭の、ＭＰ法により算出される、細孔径が０．４～２ｎｍの細孔の細孔容積が０．４０～０．５５ｃｃ／ｇの範囲であり、かつ、前記細孔容積は、ＭＰ法およびＢＪＨ法により算出される、前記活性炭の全細孔の細孔容積に対する比率が７５％以上である、ガス吸着剤。     A gas adsorbent containing activated carbon
    The pore volume of the activated carbon having a pore diameter of 0.4 to 2 nm calculated by the MP method is in the range of 0.40 to 0.55 cc / g, and the pore volume is MP. A gas adsorbent having a ratio of the activated carbon to the pore volume of all pores, calculated by the method and the BJH method, of 75% or more.
  2. 　前記活性炭の含有量が、前記ガス吸着剤の全体に対し、２０質量％以上である、請求項１に記載のガス吸着剤。 The gas adsorbent according to claim 1, wherein the content of the activated carbon is 20% by mass or more based on the total content of the gas adsorbent.
  3. 　さらに、化学反応によりアルデヒドを吸着する化学吸着剤を含む、請求項１または２に記載のガス吸着剤。 The gas adsorbent according to claim 1 or 2, further comprising a chemisorbent that adsorbs an aldehyde by a chemical reaction.
  4. 　トルエン飽和吸着後の脱離率が２５％以下である、請求項１～３のいずれか１項に記載のガス吸着剤。 The gas adsorbent according to any one of claims 1 to 3, wherein the desorption rate after saturated toluene adsorption is 25% or less.
  5. 　請求項１～４のいずれか１項に記載のガス吸着剤を含む、ガス吸着シート。 A gas adsorption sheet containing the gas adsorbent according to any one of claims 1 to 4.
  6. 　請求項１～４のいずれか１項に記載のガス吸着剤が、２層以上の不織布により形成される１つ以上の層間の少なくとも１つに保持されている、濾材。 A filter medium in which the gas adsorbent according to any one of claims 1 to 4 is held in at least one of one or more layers formed of two or more layers of non-woven fabric.
  7. 　請求項６に記載の濾材を備える、エアフィルター。 An air filter comprising the filter medium according to claim 6.
PCT/JP2020/013174 2019-03-29 2020-03-24 Gas adsorbent WO2020203508A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020518099A JPWO2020203508A1 (en) 2019-03-29 2020-03-24

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-066801 2019-03-29
JP2019066801 2019-03-29

Publications (1)

Publication Number Publication Date
WO2020203508A1 true WO2020203508A1 (en) 2020-10-08

Family

ID=72668162

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/013174 WO2020203508A1 (en) 2019-03-29 2020-03-24 Gas adsorbent

Country Status (2)

Country Link
JP (1) JPWO2020203508A1 (en)
WO (1) WO2020203508A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202100007346A1 (en) * 2021-03-25 2022-09-25 Nikitex S R L NON-WOVEN FABRIC FOR THE INTERNAL COVERING OF TRANSPORT MEANS SUITABLE FOR ADSORBING VOLATILE ORGANIC COMPOUNDS

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013150647A (en) * 2012-01-24 2013-08-08 Toyobo Co Ltd Low desorption deodorant and deodorizing filter using the same
WO2017146044A1 (en) * 2016-02-23 2017-08-31 ソニー株式会社 Solidified porous carbon material and production method thereof
WO2018116858A1 (en) * 2016-12-19 2018-06-28 株式会社アドール Active carbon and production method thereof
JP2018167155A (en) * 2017-03-29 2018-11-01 東レ株式会社 Adsorbent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013150647A (en) * 2012-01-24 2013-08-08 Toyobo Co Ltd Low desorption deodorant and deodorizing filter using the same
WO2017146044A1 (en) * 2016-02-23 2017-08-31 ソニー株式会社 Solidified porous carbon material and production method thereof
WO2018116858A1 (en) * 2016-12-19 2018-06-28 株式会社アドール Active carbon and production method thereof
JP2018167155A (en) * 2017-03-29 2018-11-01 東レ株式会社 Adsorbent

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202100007346A1 (en) * 2021-03-25 2022-09-25 Nikitex S R L NON-WOVEN FABRIC FOR THE INTERNAL COVERING OF TRANSPORT MEANS SUITABLE FOR ADSORBING VOLATILE ORGANIC COMPOUNDS

Also Published As

Publication number Publication date
JPWO2020203508A1 (en) 2020-10-08

Similar Documents

Publication Publication Date Title
JP5048454B2 (en) Adsorption / desorption element, carbon dioxide concentration adjusting device using the same, carbon dioxide concentration adjusting system, and carbon dioxide concentration adjusting method.
US7052533B2 (en) Filter element, method for manufacture thereof, and filter using said element
JP6988477B2 (en) Filter media for air purification
JP4953594B2 (en) Allergen removal filter, composite filter and filter element
JP2007069198A (en) Filter medium for gas removal, composite filter and filter element
JP5334364B2 (en) Gas removal filter medium, composite filter and filter element
JPWO2019151283A1 (en) Manufacturing method of gas adsorbent, deodorant fiber sheet and gas adsorbent
JP2015029770A (en) Air cleaning filter medium
JP6894103B2 (en) Deodorant filter and air purifier equipped with the deodorant filter
WO2020203508A1 (en) Gas adsorbent
WO2023054012A1 (en) Gas adsorbent and gas adsorption sheet, filter medium, and air filter using same
JP2004050151A (en) Gas purifying material
JP6115413B2 (en) Filter element
JPH057725A (en) Deodorizing filter
JPH11156124A (en) Honeycomb-shaped air cleaning filter
JP2019166515A (en) Air filter filter-material and air filter
JP5172165B2 (en) Gas removal filter medium, composite filter and filter element
JPH07241491A (en) Air cleaning filter
WO2024090205A1 (en) Gas adsorbent and gas adsorption sheet, filter material, and air filter using same
JP2021142481A (en) Gas adsorbent
JP2009028718A (en) Air filter medium, air filter, and air purification device
JP2000153131A (en) Dust removing/deodorizing filter using photocatalyst
JP7017026B2 (en) Deodorizing filter media and filters
JPS63137725A (en) Filter for cleaning air
JP2021112694A (en) Filter medium for air filter, and air filter unit using the same

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2020518099

Country of ref document: JP

Kind code of ref document: A

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

Ref document number: 20783037

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20783037

Country of ref document: EP

Kind code of ref document: A1