WO2021193137A1 - Filter medium - Google Patents

Filter medium Download PDF

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Publication number
WO2021193137A1
WO2021193137A1 PCT/JP2021/010024 JP2021010024W WO2021193137A1 WO 2021193137 A1 WO2021193137 A1 WO 2021193137A1 JP 2021010024 W JP2021010024 W JP 2021010024W WO 2021193137 A1 WO2021193137 A1 WO 2021193137A1
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WO
WIPO (PCT)
Prior art keywords
activated carbon
exchange resin
filter medium
porous body
inorganic porous
Prior art date
Application number
PCT/JP2021/010024
Other languages
French (fr)
Japanese (ja)
Inventor
林俊輝
浅田康裕
三好賢吾
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 KR1020227024815A priority Critical patent/KR20220153577A/en
Priority to JP2021529400A priority patent/JPWO2021193137A1/ja
Priority to CN202180022795.4A priority patent/CN115243780A/en
Publication of WO2021193137A1 publication Critical patent/WO2021193137A1/en

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Classifications

    • 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
    • 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
    • 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
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2055—Carbonaceous material
    • B01D39/2058—Carbonaceous material the material being particulate
    • B01D39/2062—Bonded, e.g. activated carbon blocks
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/30—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being formed of particles, e.g. chips, granules, powder

Definitions

  • the present invention relates to a filter medium having deodorizing performance, and particularly to a filter medium having excellent deodorizing performance for polar gas components.
  • Activated carbon cannot efficiently deodorize polar gases such as ammonia and aldehydes because it adsorbs malodorous components by physical adsorption. On the other hand, since these gases have a low threshold value, it is an issue to efficiently remove these gases in order to improve the comfort of the living environment.
  • Activated carbon is generally used to remove non-polar gas, and it is known in previous studies that it is better to have a small pore diameter to suppress secondary odor.
  • Patent Documents 1 and 2 As a method for efficiently removing gases such as aldehydes, a composite adsorbent in which silica gel carrying acid hydrazides is mixed with activated carbon has been proposed, and a filter medium using this composite adsorbent is known.
  • Patent Documents 1 and 2 This adsorbent has excellent adsorption performance for low boiling point aldehydes, high boiling point aldehydes and hydrocarbon gases.
  • the present invention has been made against the above-mentioned problems, and efficiently removes polar gases such as ammonia and aldehydes, and suppresses the secondary odor of these gases once adsorbed by the adsorbent.
  • the subject is to provide a filter medium.
  • the filter medium of the present invention for solving the above problems has at least two laminated non-woven fabrics, and is an inorganic porous body in which at least acid hydrazides are supported between at least one layer between the laminated non-woven fabrics. Contains acidic cation exchange resin.
  • the filter medium of the present invention preferably satisfies any of the following (1) to (6).
  • the acidic cation exchange resin is in the form of particles.
  • the average particle size of the acidic cation exchange resin is 200 ⁇ m or less.
  • Activated carbon is contained in at least one of the layers of the laminated non-woven fabric.
  • the pore volume of the pores having a pore diameter of 0.4 nm or more and 2 nm or less calculated by the MP method is in the range of 0.40 cc / g or more and 0.55 cc / g or less.
  • the ratio of the pore volume of the pores having a pore diameter of 0.4 nm or more and 2 nm or less to the pore volume of the pores having a pore diameter of 0.4 nm or more calculated by the MP method and the BJH method is 75. % Or more.
  • the above-mentioned activated carbon is an alkali-impregnated activated carbon.
  • Acetic acid, ammonia, and acetaldehyde gas which are designated as target gases for deodorizing performance in the air purifier standard JEMA1467, can be efficiently removed, and the secondary odor of these gases once adsorbed by the adsorbent can be suppressed.
  • the filter medium of the present invention has at least two laminated non-woven fabrics, and is characterized by containing an inorganic porous body in which at least an amine compound is supported and an ion exchange resin between the layers of the two non-woven fabrics. ..
  • the polar gas once adsorbed and separated from the inorganic porous body on which the amine compound is supported can be adsorbed by the ion exchange resin, and the secondary odor can be suppressed.
  • the inorganic porous body used in the present invention is activated carbon, zeolite, activated alumina, silica gel, activated clay, aluminum silicate, or magnesium silicate.
  • adsorbent used in the present invention two or more kinds selected from the group consisting of activated carbon, zeolite, activated alumina, silica gel, activated clay, aluminum silicate, and magnesium silicate can be used in combination.
  • the amine-supported inorganic porous body in which an amine-based compound is supported on these inorganic porous bodies is said to be effective for aldehyde-based odorous substances.
  • Examples of the amine compound supported on the inorganic porous body include aniline having an amino group, acid hydrazides, benzylamine, naphthylamine, cyclohexylamine, (iso) propanolamine, ethanolamine, and diethylenetriamine as primary amine compounds.
  • Compounds such as triethylenetetramine, ethyl styrene methacrylate, amine styrene acrylate, monomers, oligomers, polymers, derivatives containing amino groups derived from these compounds, and the like can be used.
  • Amine compounds other than primary amine compounds include ethylaniline, diethylamine, methylvinylamine, methylmethylamine styrene acrylate, vinylbenzylmethylamine, ethylmethylamine styrene methacrylate and the like. Examples thereof include compounds, monomers, oligomers, polymers, and secondary amine compounds derived from these compounds.
  • tertiary amine compound examples include vinylbenzyldimethylamine, vinylbenzyldiethylamine, diethylamine styreneacrylic acid, diethylamine styrene methacrylate, dimethylamine styreneacrylic acid, dimethylamine styrenemethacrylate, ethyldimethylamine styrene methacrylate, and styreneacrylic acid.
  • Examples thereof include compounds such as ethyldimethylamine, ethyldiethylamine styrene methacrylate, ethyldiethylamine styreneacrylate, and triethylamine, monomers, oligomers, polymers, and tertiary amine compounds derived from these compounds.
  • a primary amine compound having an amino group is preferable, and acid hydrazides are more preferable, among these, because the desorption suppressing performance of the high boiling point aldehyde of the adsorbent becomes more excellent.
  • silica gel does not react with acid hydrazides and can suppress the deterioration of acid hydrazides supported on silica gel.
  • silica gel has strong hydrophilicity and is water-soluble such as acid hydrazides.
  • the inorganic porous body is preferably silica gel because it has a high affinity with a drug and can improve the adsorption performance of the aldehyde of the adsorbent.
  • the inorganic porous body used in the present invention is preferably in the form of particles. If it is in the form of particles, it is preferable because it is possible to achieve both performance and economy.
  • the fibrous inorganic porous body has an increased specific surface area, higher contact efficiency with the target gas, and better performance (removal efficiency), but is not effective in consideration of economy because of its high price.
  • the average particle size of the inorganic porous body is preferably in the range of 50 to 1000 ⁇ m.
  • the average particle size of the inorganic porous body is preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, because the property and processability are deteriorated.
  • the average particle size of the inorganic porous body is preferably 1000 ⁇ m or less, and more preferably 600 ⁇ m or less.
  • the average particle size referred to here refers to the mass average particle size specified in the JIS-K1474 (2014) activated carbon test method.
  • the average pore diameter of the inorganic porous material used in the present invention is preferably 40 to 500 angstroms.
  • the average pore diameter of the inorganic porous body is more preferably 300 angstroms or less.
  • the average pore diameter of the inorganic porous body is preferably 50 angstroms or more.
  • the specific surface area of the inorganic porous body used in the present invention is preferably 30 to 1000 m 2 / g in terms of BET specific surface area.
  • the specific surface area of the inorganic porous body is set to 30 m 2 / g or more, the effective area as a reaction field of the amine compound supported by the inorganic porous body is improved, and the adsorbent and the VOC gas to be removed are used. Reaction speed is improved.
  • the BET specific surface area of the inorganic porous body is more preferably 50 m 2 / g or more.
  • the BET specific surface area of the inorganic porous body is 1000 m 2 / g or less, it is possible to suppress a decrease in handleability due to a decrease in mechanical strength of the inorganic porous body, and a VOC gas leading to secondary odor can be suppressed. It is possible to suppress unintentional adsorption to the adsorbent.
  • the inorganic porous body used in the present invention carries acid hydrazides as an amine compound for removing low boiling point aldehydes contained in VOC gas. Further, the acid hydrazides are preferably water-soluble acid hydrazides from the viewpoint of easy support processing on the inorganic porous body.
  • water-soluble acid hydrazides refer to acid hydrazides that dissolve in 0.5% by mass or more with respect to water (25 ° C.).
  • Acid hydrazides are compounds having an acid hydrazide group represented by -CO-NHNH 2 derived from a carboxylic acid and hydrazine, and a nitrogen atom having an unshared electron pair at the ⁇ -position at the hydrazide terminal. Is bound, which significantly improves the nucleophilic reactivity. This unshared electron pair reacts by nucleophilically attacking the carbonyl carbon atom of an aldehyde compound (aldehyde compound is a concept including low boiling point aldehyde and high boiling point aldehyde), and fixes the aldehyde compound as a hydrazine derivative. It is considered that the adsorption performance of the aldehyde compound can be exhibited by the conversion.
  • acetaldehyde has an electron-donating alkyl group at the ⁇ -position of the carbonyl carbon, so that the electrophile of the carbonyl carbon is low and it is difficult to be chemically adsorbed.
  • the acid hydrazide used in the gas adsorbent used in the present invention As mentioned above, since the class has high electrophilic reactivity, it exhibits good chemisorption performance even for acetaldehyde.
  • acid hydrazides include those containing one or more selected from the group consisting of carbodihydrazide, glutamic acid dihydrazide, succinic acid dihydrazide, and adipic acid dihydrazide.
  • adipic acid dihydrazide is particularly preferable because it has excellent adsorption performance for aldehyde compounds. Further, it is more preferable to use adipic acid dihydrazide and succinic acid dihydrazide in combination for the purpose of improving the adsorption performance of the aldehyde compound.
  • the amount of the acid hydrazides used in the present invention is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the inorganic porous body.
  • the content of acid hydrazides is 1 part by mass or more, the adsorption performance of the aldehyde compound of the adsorbent can be further improved.
  • the amount of acid hydrazides supported is more preferably 3 parts by mass or more.
  • the method for supporting the acid hydrazides on the inorganic porous body is not particularly limited as long as it is a method that can obtain desired characteristics.
  • the inorganic porous body is contained in an aqueous solution in which the acid hydrazides are dissolved.
  • a method of supporting acid hydrazides on an inorganic porous body by adding and dispersing acid hydrazides, or an aqueous solution in which acid hydrazides are dissolved in a solvent is sprayed and applied to the inorganic porous body, and then this inorganic porous body is sprayed and applied. Examples include a method of drying the body.
  • an appropriate solvent can be selected in consideration of the characteristics and workability of acid hydrazides.
  • an aqueous solvent from the viewpoint of safety and workability, and it is more preferable to use pure water as the solvent.
  • the inorganic porous body carrying the acid hydrazides used in the present invention preferably has a pH in the range of 3.0 to 7.5 when 5 g is dispersed in 100 g of water at 25 ° C.
  • the pH is 7.5 or less, the intermediate produced from the reaction by the nucleophilic attack on the carbonyl carbon atom of the aldehyde compound of the unshared electron pair of acid hydrazides is protonated in the acidic reaction field. Therefore, it becomes easy to dehydrate, and the immobilization reaction of the intermediate to the derivative proceeds sufficiently.
  • the pH is more preferably 6.5 or less.
  • the unshared electron pair of acid hydrazides becomes more active in nucleophilically attacking the carbonyl carbon atom of the aldehyde compound, and the adsorption performance of the aldehyde compound of the adsorbent becomes higher. Becomes better.
  • the pH was measured by immersing the inorganic porous body carrying acid hydrazides in pure water at 25 ° C. so as to be 5% by mass, stirring lightly, and then leaving it for 10 minutes, and measuring the pH of the liquid with a pH meter. To say.
  • the pH of the inorganic porous body carrying acid hydrazides can be adjusted by adding an organic acid.
  • an organic acid it is preferable to use an organic acid that does not generate an odor by itself and has low hygroscopicity.
  • Specific examples of the organic acid as described above include adipic acid, sulfanic acid, malic acid, citric acid and the like, which may be appropriately selected according to the acid hydrazides used, and adipic acid is preferably adopted. be able to.
  • an acidic cation exchange resin is used as an alternative to the organic acid. Acidic cation exchange resins are preferable because they do not generate their own odor or hygroscopicity.
  • acid hydrazides have excellent reactivity with acetaldehyde, which is abundant in tobacco smoke, so that the effect of significantly reducing the pungent odor peculiar to tobacco can be obtained.
  • the hydrazide compound can be arbitrarily selected from the above-mentioned adipic acid dihydrazide, dodecanedioic acid dihydrazide, succinate dihydrazide and the like. Among them, adipic acid dihydrazide is more preferable because it exhibits an appropriate solubility and the adsorbent can be easily attached to the micropores.
  • the filter medium of the present invention contains an ion exchange resin in addition to an inorganic porous body in which an amine compound is supported between layers of the non-woven fabric in order to efficiently remove the target gas regardless of whether it is a polar or non-polar gas. There is.
  • the ion exchange resin is not particularly limited, and is a strongly acidic cation exchange resin or a weakly acidic cation exchange resin capable of effectively chemically adsorbing a basic gas, or a strongly basic anion exchange resin or a weak base capable of effectively chemically adsorbing an acidic gas.
  • a strongly acidic cation exchange resin or a weakly acidic cation exchange resin capable of effectively chemically adsorbing a basic gas
  • a strongly basic anion exchange resin or a weak base capable of effectively chemically adsorbing an acidic gas.
  • an amphoteric ion exchange resin or the like can be used.
  • the base of the ion exchange resin is usually a copolymer of styrene and divinylbenzene, and depending on its base structure, it is roughly divided into a transparent and almost homogeneous gel type and a macroporous type having a physically large pore size.
  • any ion exchange resin can be used.
  • a strongly acidic cation exchange resin using a sulfonic acid group as an exchange group a weakly acidic cation exchange resin using a carboxyl group or a phenol hydroxyl group as an exchange group
  • a strongly basic anion exchange resin using a quaternary ammonium base as an exchange group.
  • Examples thereof include weakly basic anion exchange resins using first, second and third amines as exchange groups.
  • a basic odor component such as ammonia
  • the acidic cation exchange resin used in the present invention is preferably in the form of particles. If it is in the form of particles, it is preferable because it is possible to achieve both performance and economy.
  • the fibrous acidic cation exchange resin increases the specific surface area, increases the contact efficiency with the target gas, and improves the performance (removal efficiency), but it is not effective in consideration of economy because of its high price.
  • the average particle size of the acidic cation exchange resin used in the present invention is preferably 1000 ⁇ m or less, but the smaller the average particle size of the acidic cation exchange resin, the faster the adsorption rate of the adsorbent gas, and therefore 200 ⁇ m or less is more preferable. ..
  • the lower limit of the average particle size is not particularly limited, but if the average particle size is less than 100 ⁇ m, the particles tend to scatter and the handleability and processability of the acid cation exchange resin tend to deteriorate. Therefore, the average particles of the acid cation exchange resin are average particles.
  • the diameter is preferably 50 ⁇ m or more, and more preferably 100 ⁇ m or more.
  • the average particle size referred to here refers to the mass average particle size measured by the activated carbon test method specified in JIS-K1474 (2014).
  • the content ratio of the acidic cation exchange resin to the inorganic porous body carrying the acid hydrazides used in the present invention is preferably in the range of 10 to 300%.
  • the content ratio of the acidic cation exchange resin is more preferably 30% or more.
  • the filter medium of the present invention preferably contains activated carbon in addition to the inorganic porous body in which the amine compound is supported and the ion exchange resin between the layers of the non-woven fabric.
  • activated carbon those made from coconut shell, coal, wood flour, phenol resin and the like are preferable.
  • granular activated carbon having a relatively small particle size which is commercialized through steps such as firing, washing, pulverization, and spheroidization, is preferable.
  • the activated carbon used in the filter medium of the present invention preferably has the following pore structure. That is, the pore volume of the pores having a pore diameter of 0.4 nm or more and 2 nm or less calculated by the MP method is in the range of 0.40 cc / g or more and 0.55 cc / g or less, and the MP method and The ratio of the pore volume of the pores having a pore diameter of 0.4 nm or more and 2 nm or less to the pore volume of the pores having a pore diameter of 0.4 nm or more calculated by the BJH method is 75% or more. Is preferable. A more preferable volume ratio is 85% or more.
  • the pore volume formed by the pores of a specific size is in a specific range, that is, a specific number of pores of a specific size are present in the activated carbon, and further.
  • the ratio of the pore volume of pores having a pore diameter of 0.4 nm or more and 2 nm or less to the pore volume of pores of 0.4 nm or more is 75% or more, that is, the pore diameter is finer than 2 nm.
  • the adsorbent having this activated carbon can adsorb and remove odorous components such as toluene. It has excellent performance, and the desorption of odorous components such as toluene once adsorbed from the adsorbent is suppressed.
  • the MP (MICROPORE) method is an analysis method that can quantify the distribution of micropores in the pore size of activated carbon.
  • a method for analyzing the pore diameter and pore volume of the pore diameter of activated carbon there are MP (MICROPORE) method, BJH (Barrett-Joiner-Halenda) method, and the like.
  • the MP method suitable for analysis in this range is 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 is adopted for the analysis of macropores having a pore diameter exceeding 2 nm.
  • the pore volume of the pore having a pore diameter of 0.4 nm or more calculated by the MP method and the BJH method in the present invention is obtained by the value of the pore volume obtained by the MP method and the BJH method. It means the total value of the pore volume values.
  • alkali metal compounds have high reactivity with acid-based gases such as acetic acid, alleviate the acid-based "sour odor", and can change the odor that is difficult for the user to perceive.
  • the alkali metal compound can be arbitrarily selected from potassium hydroxide, potassium carbonate, sodium hydrogen carbonate and the like.
  • activated carbon impregnated with an alkali metal compound is referred to as alkaline impregnated activated carbon.
  • the activated carbon, the inorganic porous body carrying acid hydrazides, and the cation exchange resin may be arranged in any arrangement, either in the same layer or in different layers, but when the activated carbon impregnated with alkali is contained.
  • the above-mentioned adsorbent is supported between layers of the non-woven fabric.
  • the form of the non-woven fabric at that time is not particularly limited, and examples thereof include chemical-bonded non-woven fabrics, wet paper-made non-woven fabrics, spunbonded non-woven fabrics, melt-blown non-woven fabrics, spunlaced non-woven fabrics, and air-laid non-woven fabrics.
  • a particulate adsorbent uniformly mixed with a heat-adhesive material having a particle size equivalent to that of the adsorbent is uniformly mixed on one flat surface of the non-woven fabric.
  • the heat-adhesive material used at that time is such as fibers, particles, and powder made of a thermoplastic resin such as a polyester resin, a polyamide resin, a polyolefin resin, and a modified resin thereof.
  • the pore volume of pores having a pore diameter of 0.4 nm or more and 2 nm or less was calculated. Specifically, the pore volume of pores having a pore diameter of 0.4 nm or more and 2 nm or less was determined by the MP method. For the pore volume having a pore diameter of 0.4 nm or more, the pore volume of the pore having a pore diameter exceeding 2 nm is calculated by the BJH method, and this volume and the pore diameter obtained by the above-mentioned MP method are 0.4 nm or more. The pore volume of 2 nm or less was added.
  • Secondary odor test (secondary odor (points) and comfort / discomfort (points))
  • the evaluation filter medium frontage dimensions 20 cm ⁇ 20 cm obtained by the above-mentioned method of manufacturing the filter medium was placed in a test chamber made of clear acrylic volume 1 m 3, by burning tobacco (Moebius 10 mg) 5 present in the test chamber, the combustion fumes was collected on a filter medium for 30 minutes. This work was repeated 10 times to collect a total of 50 cigarette smokes.
  • the evaluation filter medium after collecting the tobacco combustion smoke was placed in a checked plastic bag having dimensions: 200 x 280 mm and a thickness of 0.04 mm, and 1 L of clean air was further put into the bag. After that, the check of the plastic bag was closed, and the inside of the bag was kept in a sealed state for 6 hours.
  • the odor intensity and the degree of comfort and discomfort of the air discharged from the adjusted plastic bag were scored by five panelists according to the criteria shown in Tables 3 and 4, and the average value was calculated.
  • Example 1 (Inorganic porous body) As the inorganic porous body, porous silica (Fuji Silysia Chemical Ltd.) having an average particle diameter of 300 ⁇ m was used. (Adhesive) Low-density polyethylene (Tokyo Ink Co., Ltd.) was used as the adhesive. (Melting point 98-104 degrees) (Amine compound) Adipic acid dihydrazide (Nippon Kasei Chemical Company Limited) was used as the amine compound.
  • Aldehyde adsorbent An aqueous solution prepared by dissolving the above-mentioned adipic acid dihydrazide in 7% by mass of water and an inorganic porous body were mixed and dried to prepare an aldehyde adsorbent.
  • ion exchange resin As the ion exchange resin, a strongly acidic cation exchange resin having an average particle diameter of about 150 ⁇ m was used.
  • Activated carbon As the activated carbon, sodium hydrogen carbonate-impregnated activated carbon having an average particle size of 230 ⁇ m was used.
  • the production conditions for the activated carbon impregnated with sodium hydrogen carbonate are as follows.
  • the ratio of the pore volume of the pores having a pore diameter of 0.4 to 2 nm to the pore volume of the pores was 86%.
  • Non-woven fabric A As the non-woven fabric A, a wet papermaking non-woven fabric was used.
  • Non-woven fabric B As the non-woven fabric B, a melt-blown non-woven fabric was used.
  • Manufacturing method of filter media The filter medium was prepared by the following manufacturing method.
  • a blend of 100 parts by mass of an aldehyde adsorbent, 90 parts by mass of an adhesive, 100 parts by mass of an ion exchange resin and 100 parts by mass of activated carbon impregnated with sodium hydrogen carbonate is uniformly sprayed on the non-woven fabric A, and the temperature is increased from 110 ° C. in a heating furnace.
  • the adhesive was melted by heating at 130 ° C. After laminating the non-woven fabric B on the sprayed surface, the non-woven fabric B was pressed by a nip roll to produce a filter medium.
  • Example 2 Aldehyde adsorbent The same as in Example 1 was used. (glue) The same as in Example 1 was used. (Ion exchange resin) The same as in Example 1 was used. (Activated carbon) The same as in Example 1 was used. (Non-woven fabric A) The same as in Example 1 was used. (Non-woven fabric B) The same as in Example 1 was used. (Non-woven fabric C) As the non-woven fabric C, a melt-blown non-woven fabric was used. (Manufacturing method of filter media) The filter medium was prepared by the following manufacturing method.
  • Example 3 Aldehyde adsorbent The same as in Example 1 was used. (glue) The same as in Example 1 was used. (Ion exchange resin) The same as in Example 1 was used. (Activated carbon) As the activated carbon, unimpregnated activated carbon A (average particle size 230 ⁇ m) was used. (Non-woven fabric A) The same as in Example 1 was used. (Non-woven fabric B) The same as in Example 1 was used. (Filter material) As for the composition of the filter medium, the one under the following conditions was used.
  • Example 4 Aldehyde adsorbent The same as in Example 1 was used. (glue) The same as in Example 1 was used. (Ion exchange resin) The same as in Example 1 was used. (Activated carbon) As the activated carbon, unattached activated carbon B (average particle size 230 ⁇ m, pore volume of pores having a pore diameter of 0.4 to 2 nm calculated by the MP method is 0.39 cc / g, calculated by the MP method and the BJH method). The ratio of the pore volume of the pores having a pore diameter of 0.4 to 2 nm to the pore volume of the pores having a pore diameter of 0.4 nm or more was 75%) was used.
  • Non-woven fabric A The same as in Example 1 was used.
  • Non-woven fabric B The same as in Example 1 was used.
  • (Filter material) As for the composition of the filter medium, the one under the following conditions was used. Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 90 parts by mass of an adhesive, 100 parts by mass of an ion exchange resin and 100 parts by mass of unattached activated carbon B are interposed between the nonwoven fabric A and the nonwoven fabric B.
  • Example 5 (Aldehyde adsorbent) The same as in Example 1 was used. (glue) The same as in Example 1 was used. (Ion exchange resin) The same as in Example 1 was used. (Activated carbon) As the activated carbon, unattached activated carbon C (average particle size 230 ⁇ m, pore volume of pores having a pore diameter of 0.4 to 2 nm calculated by the MP method is 0.40 cc / g, calculated by the MP method and the BJH method). The ratio of the pore volume of the pores having a pore diameter of 0.4 to 2 nm to the pore volume of the pores having a pore diameter of 0.4 nm or more was 51%) was used.
  • Non-woven fabric A The same as in Example 1 was used.
  • Non-woven fabric B The same as in Example 1 was used.
  • (Filter material) As for the composition of the filter medium, the one under the following conditions was used. Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 90 parts by mass of an adhesive, 100 parts by mass of an ion exchange resin and 100 parts by mass of unattached activated carbon C are interposed between the nonwoven fabric A and the nonwoven fabric B.
  • Example 6 Aldehyde adsorbent The same as in Example 1 was used. (glue) The same as in Example 1 was used. (Ion exchange resin) As the ion exchange resin, a strongly acidic cation exchange resin having an average particle diameter of about 650 ⁇ m was used. (Activated carbon with sodium hydrogen carbonate) The same as in Example 1 was used. (Non-woven fabric A) The same as in Example 1 was used. (Non-woven fabric B) The same as in Example 1 was used. (Filter material) As for the composition of the filter medium, the one under the following conditions was used.
  • Example 7 Aldehyde adsorbent
  • glue The same one used in Example 1 was used.
  • Ion exchange resin The same as in Example 6 was used.
  • Activated carbon The same as in Example 3 was used.
  • Non-woven fabric A The same as in Example 1 was used.
  • Non-woven fabric B The same as in Example 1 was used.
  • Filter material As for the composition of the filter medium, the one under the following conditions was used.
  • Example 8 Aldehyde adsorbent
  • glue The same as in Example 1 was used.
  • Ion exchange resin The same as in Example 6 was used.
  • Non-woven fabric A The same as in Example 1 was used.
  • Non-woven fabric B The same as in Example 1 was used.
  • Comter material As for the composition of the filter medium, the one under the following conditions was used. Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 60 parts by mass of an adhesive and 100 parts by mass of an ion exchange resin are interposed between the layers of the non-woven fabric A and the non-woven fabric B.
  • Example 9 (Aldehyde adsorbent) The same as in Example 1 was used. (glue) The same as in Example 1 was used. (Ion exchange resin) The same as in Example 1 was used. (Non-woven fabric A) The same as in Example 1 was used. (Non-woven fabric B) The same as in Example 1 was used. (Filter material) As for the composition of the filter medium, the one under the following conditions was used. Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 60 parts by mass of an adhesive and 100 parts by mass of an ion exchange resin are interposed between the layers of the non-woven fabric A and the non-woven fabric B.
  • Example 10 Aldehyde adsorbent
  • glue The same as in Example 1 was used.
  • Ion exchange resin The same as in Example 1 was used.
  • Non-woven fabric A The same as in Example 1 was used.
  • Non-woven fabric B The same as in Example 1 was used.
  • Non-woven fabric C The same as in Example 2 was used.
  • Filter material As for the composition of the filter medium, the one under the following conditions was used.
  • Example 1 (Inorganic porous body) The same as in Example 1 was used. (glue) The same as in Example 1 was used. (Ion exchange resin) The same as in Example 3 was used. (Activated carbon) The same as in Example 3 was used. (Non-woven fabric A) The same as in Example 1 was used. (Non-woven fabric B) The same as in Example 1 was used. (Filter material) As for the composition of the filter medium, the one under the following conditions was used.
  • Example 2 (Aldehyde adsorbent) The same as in Example 1 was used. (glue) The same as in Example 1 was used. (Activated carbon) Example 3 The same thing was used. (Non-woven fabric A) The same as in Example 1 was used. (Non-woven fabric B) The same as in Example 1 was used. (Filter material) As for the composition of the filter medium, the one under the following conditions was used. Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 100 parts by mass of unattached activated carbon and 60 parts by mass of an adhesive are interposed between the nonwoven fabric A and the nonwoven fabric B.
  • Table 1 summarizes the configurations and characteristics of the filter media of each example and comparative example.
  • the filter media of Examples 1 to 10 have an inorganic porous body impregnated with acid hydrazides as an amine compound, excellent results in deodorizing performance of acetaldehyde can be obtained, and they have an ion exchange resin. The results of excellent deodorizing performance of ammonia were obtained, and the degree of odor was low in all cases.
  • the filter media of Examples 1 to 7 had activated carbon, the results obtained that the deodorizing performance of acetic acid was superior to that of the filter media of Examples 8 to 10 having no activated carbon.
  • the filter media of Examples 1, 2 and 6 have activated carbon impregnated with sodium hydrogen carbonate, they are further compared with the filter media of Examples 3, 4, 5 and 7 not impregnated with sodium hydrogen carbonate. The result was that the deodorizing performance of acetic acid was excellent.
  • the filter media of Examples 1, 2, 3, 4, 5, 9 and 10 have an ion exchange resin having a small particle size
  • the filter media of Examples 6 to 8 have an ion exchange resin having a large particle size. In comparison, the results obtained that the deodorizing performance of ammonia was excellent.
  • Example 2 Compared with Example 1, in Example 2, the activated carbon impregnated with sodium hydrogen carbonate, the aldehyde adsorbent, and the ion exchange resin are arranged in different layers, so that the activated carbon and the chemicals adhering to the aldehyde are not affected by each other. Results were obtained that were effective in deodorizing performance and suppressing secondary odor.
  • the pore volume of pores having a pore diameter of 0.4 to 2 nm calculated by the MP method as unattached activated carbon is 0.42 cc / g, and the pore diameter calculated by the MP method is 0.4 nm. Since activated carbon is used in which the ratio of the pore volume of the pores having a pore diameter of 0.4 to 2 nm to the pore volume of the above pores is 86%, it is compared with Examples 4 and 5 and is secondary. The result of suppressing the odor was obtained.
  • Example 9 Since the filter medium of Example 9 has an aldehyde adsorbent and an ion exchange resin in the same layer, ammonia and acetaldehyde are compared with the filter medium having no aldehyde adsorbent and an ion exchange resin in the same layer of Example 10. The results obtained that the secondary odor was suppressed by efficiently removing the gas and removing these gases once adsorbed by the adsorbent by the other adsorbent interposed in the same layer.
  • the filter medium of Comparative Example 1 does not have an aldehyde adsorbent, the deodorizing performance of aldehyde is inferior, and the filter medium of Comparative Example 2 does not have an ion exchange resin, so that the deodorizing performance of ammonia is poor. Inferior results were obtained, and both had a high degree of odor.
  • the filter medium of the present invention has excellent adsorption performance for polar gases such as ammonia and aldehydes, and has few problems of secondary odor during long-term use.
  • it is preferably used as an air filter for purifying pet odor air, which is regarded as a problem as indoor odor in facilities for the elderly.

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Abstract

The present invention addresses a problem associated with conventional filter media that utilize activated carbon, i.e. the problem of improving the performance to deodorize polar gases such as ammonia and aldehydes. Specifically, the present invention addresses the problem of providing a high-performance adsorbent which utilizes chemical adsorption instead of physical adsorption, and which is not susceptible to desorption of a bad odor component that has adsorbed thereto. The present invention is characterized by: comprising at least two nonwoven fabrics stacked upon each other; and containing an acidic cation exchange resin and an inorganic porous body that supports at least an acid hydrazide in at least one space between the stacked nonwoven fabrics.

Description

濾材Filter media
　本発明は、脱臭性能を有する濾材に関し、特に極性ガス成分に対する脱臭性能に優れる濾材に関する。 The present invention relates to a filter medium having deodorizing performance, and particularly to a filter medium having excellent deodorizing performance for polar gas components.
　活性炭では、物理吸着により悪臭成分を吸着するため、アンモニアやアルデヒド類といった極性ガスを効率的に脱臭できない。一方でこれらのガスは閾値が低いことから、生活環境の快適性を向上させる上で効率的に除去することが課題とされている。 Activated carbon cannot efficiently deodorize polar gases such as ammonia and aldehydes because it adsorbs malodorous components by physical adsorption. On the other hand, since these gases have a low threshold value, it is an issue to efficiently remove these gases in order to improve the comfort of the living environment.
　活性炭は一般的に非極性ガスの除去に用いられ、二次発臭を抑制するには細孔径が小さなものが良いとこれまでの研究で知られている。 Activated carbon is generally used to remove non-polar gas, and it is known in previous studies that it is better to have a small pore diameter to suppress secondary odor.
　アルカリ性を呈するアンモニアのように化学的性質が特定できる悪臭成分に対しては、活性炭の表面に酸を添着し中和によって脱臭除去する技術が知られている。一方で酸を添着した活性炭は吸着した有機物を酸加水分解することにより悪臭を発生させてしまう懸念があるが、有機物を吸着しないイオン交換樹脂ではそのような懸念がない。 For malodorous components whose chemical properties can be specified, such as ammonia, which exhibits alkalinity, a technique is known in which an acid is impregnated on the surface of activated carbon and deodorized and removed by neutralization. On the other hand, activated carbon impregnated with an acid may generate a foul odor by acid-hydrolyzing the adsorbed organic substance, but an ion exchange resin that does not adsorb the organic substance does not have such a concern.
　また、アルデヒド類のようなガスを効率的に除去する方法としては酸ヒドラジド類を担持したシリカゲルを、活性炭と混合した複合吸着剤が提案されており、この複合吸着剤を用いた濾材が知られている（特許文献１,２）。この吸着剤は、低沸点アルデヒド、高沸点アルデヒドおよび炭化水素系ガスの吸着性能に優れたものとなっている。 Further, as a method for efficiently removing gases such as aldehydes, a composite adsorbent in which silica gel carrying acid hydrazides is mixed with activated carbon has been proposed, and a filter medium using this composite adsorbent is known. (Patent Documents 1 and 2). This adsorbent has excellent adsorption performance for low boiling point aldehydes, high boiling point aldehydes and hydrocarbon gases.
特開２０１５－２９７７０号公報JP-A-2015-29770 特開２０１８－１６７１５５号公報JP-A-2018-167155
　しかしアンモニアやアルデヒド類といった極性ガスにおいて、一方を選択的に除去する技術は開発されているが、両方のガスを効率的に除去する方法は未だ確立されていない。 However, although technologies for selectively removing one of polar gases such as ammonia and aldehydes have been developed, a method for efficiently removing both gases has not yet been established.
　そこで、本発明は上記の課題を背景になされたものであり、アンモニアやアルデヒド類といった極性ガスを効率的に除去し、かつ吸着剤に一旦吸着されたこれらのガスの二次発臭を抑制する濾材を提供することを課題とする。 Therefore, the present invention has been made against the above-mentioned problems, and efficiently removes polar gases such as ammonia and aldehydes, and suppresses the secondary odor of these gases once adsorbed by the adsorbent. The subject is to provide a filter medium.
　上記課題を解決する本発明の濾材は、積層された少なくとも２枚の不織布を有し、前記積層された不織布の層間の少なくとも１つの層間に、少なくとも酸ヒドラジド類が担持された無機多孔質体と酸性カチオン交換樹脂を含んでいる。 The filter medium of the present invention for solving the above problems has at least two laminated non-woven fabrics, and is an inorganic porous body in which at least acid hydrazides are supported between at least one layer between the laminated non-woven fabrics. Contains acidic cation exchange resin.
　本発明の濾材は、以下の（１）～（６）のいずれかを満たすことが好ましい。
（１）上記酸性カチオン交換樹脂が粒子状である。
（２）上記酸性カチオン交換樹脂の平均粒子径が２００μｍ以下である。
（３）積層された不織布の層間の少なくとも１つに活性炭が含まれる。
（４）ＭＰ法により算出される上記活性炭の細孔径が０．４ｎｍ以上、２ｎｍ以下である細孔の細孔容積が０．４０ｃｃ／ｇ以上、０．５５ｃｃ／ｇ以下の範囲であり、かつ、ＭＰ法およびＢＪＨ法により算出される細孔径が０．４ｎｍ以上の細孔の細孔容積に対する、活性炭の細孔径が０．４ｎｍ以上、２ｎｍ以下である細孔の細孔容積の比率が７５％以上である。
（５）上記活性炭がアルカリ添着活性炭である。 The filter medium of the present invention preferably satisfies any of the following (1) to (6).
(1) The acidic cation exchange resin is in the form of particles.
(2) The average particle size of the acidic cation exchange resin is 200 μm or less.
(3) Activated carbon is contained in at least one of the layers of the laminated non-woven fabric.
(4) The pore volume of the pores having a pore diameter of 0.4 nm or more and 2 nm or less calculated by the MP method is in the range of 0.40 cc / g or more and 0.55 cc / g or less. , The ratio of the pore volume of the pores having a pore diameter of 0.4 nm or more and 2 nm or less to the pore volume of the pores having a pore diameter of 0.4 nm or more calculated by the MP method and the BJH method is 75. % Or more.
(5) The above-mentioned activated carbon is an alkali-impregnated activated carbon.
　空気清浄機規格ＪＥＭＡ１４６７において脱臭性能の対象ガスとして指定されている、酢酸、アンモニア、アセトアルデヒドガスを効率的に除去し、かつ吸着剤に一旦吸着されたこれらのガスの二次発臭を抑制できる。 Acetic acid, ammonia, and acetaldehyde gas, which are designated as target gases for deodorizing performance in the air purifier standard JEMA1467, can be efficiently removed, and the secondary odor of these gases once adsorbed by the adsorbent can be suppressed.
　以下、本発明に係る濾材の好適な実施の形態を詳細に説明する。ただし、本発明は、以下の実施の形態に限定されるものではなく、目的や用途に応じて種々に変更して実施することができる。 Hereinafter, preferred embodiments of the filter medium according to the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be variously modified and implemented according to an object and an application.
　本発明の濾材は、積層された少なくとも２枚の不織布を有し、これら２枚の不織布の層間に、少なくともアミン系化合物が担持された無機多孔質体とイオン交換樹脂を含むことを特徴とする。そうすることで、アミン系化合物が担持された無機多孔質体に一度吸着し離脱した極性ガスをイオン交換樹脂で吸着することができ、二次発臭を抑制することが可能となる。 The filter medium of the present invention has at least two laminated non-woven fabrics, and is characterized by containing an inorganic porous body in which at least an amine compound is supported and an ion exchange resin between the layers of the two non-woven fabrics. .. By doing so, the polar gas once adsorbed and separated from the inorganic porous body on which the amine compound is supported can be adsorbed by the ion exchange resin, and the secondary odor can be suppressed.
　本発明で採用する無機多孔質体としては、活性炭、ゼオライト、活性アルミナ、シリカゲル、活性白土、ケイ酸アルミニウム、またはケイ酸マグネシウムである。本発明で用いる吸着剤では、活性炭、ゼオライト、活性アルミナ、シリカゲル、活性白土、ケイ酸アルミニウム、ケイ酸マグネシウムからなる群より選ばれる２種以上を併用することもできる。そしてこれらの無機多孔質体にアミン系化合物を担持させたアミン担持無機多孔質体は、アルデヒド系臭気物に有効だとされている。 The inorganic porous body used in the present invention is activated carbon, zeolite, activated alumina, silica gel, activated clay, aluminum silicate, or magnesium silicate. In the adsorbent used in the present invention, two or more kinds selected from the group consisting of activated carbon, zeolite, activated alumina, silica gel, activated clay, aluminum silicate, and magnesium silicate can be used in combination. The amine-supported inorganic porous body in which an amine-based compound is supported on these inorganic porous bodies is said to be effective for aldehyde-based odorous substances.
　無機多孔質体に担持されるアミン系化合物としては、第１級アミン系化合物としてアミノ基を有するアニリン、酸ヒドラジド類、ベンジルアミン、ナフチルアミン、シクロヘキシルアミン、（イソ）プロパノールアミン、エタノールアミン、ジエチレントリアミン、トリエチレンテトラミン、スチレンメタクリル酸エチルアミン、スチレンアクリル酸アミン等の化合物、モノマー、オリゴマー、ポリマーあるいはこれらの化合物から誘導されるアミノ基を含有する誘導体などを用いることができる。 Examples of the amine compound supported on the inorganic porous body include aniline having an amino group, acid hydrazides, benzylamine, naphthylamine, cyclohexylamine, (iso) propanolamine, ethanolamine, and diethylenetriamine as primary amine compounds. Compounds such as triethylenetetramine, ethyl styrene methacrylate, amine styrene acrylate, monomers, oligomers, polymers, derivatives containing amino groups derived from these compounds, and the like can be used.
　第１級アミン系化合物以外のアミン系化合物、たとえば第２級アミン系化合物としては、エチルアニリン、ジエチルアミン、メチルビニルアミン、スチレンアクリル酸メチルメチルアミン、ビニルベンジルメチルアミン、スチレンメタクリル酸エチルメチルアミン等の化合物、モノマー、オリゴマー、ポリマーあるいはこれらの化合物から誘導される第２級アミン系化合物などが挙げられる。 Amine compounds other than primary amine compounds, for example, secondary amine compounds include ethylaniline, diethylamine, methylvinylamine, methylmethylamine styrene acrylate, vinylbenzylmethylamine, ethylmethylamine styrene methacrylate and the like. Examples thereof include compounds, monomers, oligomers, polymers, and secondary amine compounds derived from these compounds.
　第３級アミン系化合物としては、ビニルベンジルジメチルアミン、ビニルベンジルジエチルアミン、スチレンアクリル酸ジエチルアミン、スチレンメタクリル酸ジエチルアミン、スチレンアクリル酸ジメチルアミン、スチレンメタクリル酸ジメチルアミン、スチレンメタクリル酸エチルジメチルアミン、スチレンアクリル酸エチルジメチルアミン、スチレンメタクリル酸エチルジエチルアミン、スチレンアクリル酸エチルジエチルアミン、トリエチルアミン等の化合物、モノマー、オリゴマー、ポリマーあるいはこれらの化合物から誘導される第３級アミン系化合物などが挙げられる。吸着剤の高沸点アルデヒドの脱離抑制性能がより優れたものとなるとの理由から、これらの中では、アミノ基を有する第１級アミン系化合物が好ましく、中でも酸ヒドラジド類がより好ましい。 Examples of the tertiary amine compound include vinylbenzyldimethylamine, vinylbenzyldiethylamine, diethylamine styreneacrylic acid, diethylamine styrene methacrylate, dimethylamine styreneacrylic acid, dimethylamine styrenemethacrylate, ethyldimethylamine styrene methacrylate, and styreneacrylic acid. Examples thereof include compounds such as ethyldimethylamine, ethyldiethylamine styrene methacrylate, ethyldiethylamine styreneacrylate, and triethylamine, monomers, oligomers, polymers, and tertiary amine compounds derived from these compounds. Among these, a primary amine compound having an amino group is preferable, and acid hydrazides are more preferable, among these, because the desorption suppressing performance of the high boiling point aldehyde of the adsorbent becomes more excellent.
　無機多孔質体の中でもシリカゲルは、酸ヒドラジド類と反応することがなく、シリカゲルに担持された酸ヒドラジド類の劣化を抑制できる点に加え、シリカゲルは親水性が強く、酸ヒドラジド類などの水溶性薬剤との親和性も高く、吸着剤のアルデヒドの吸着性能をより優れたものとできる点から、無機多孔質体はシリカゲルであることが好ましい。 Among the inorganic porous bodies, silica gel does not react with acid hydrazides and can suppress the deterioration of acid hydrazides supported on silica gel. In addition, silica gel has strong hydrophilicity and is water-soluble such as acid hydrazides. The inorganic porous body is preferably silica gel because it has a high affinity with a drug and can improve the adsorption performance of the aldehyde of the adsorbent.
　また、本発明で用いる無機多孔質体は粒子状が好ましい。粒子状であれば、性能面と経済面の両立が可能であるため好ましい。繊維状の無機多孔質体は、比表面積が増加し対象ガスとの接触効率が高くなり性能面（除去効率）は良くなるが、高価格であるため経済面を考慮すると有効ではない。 Further, the inorganic porous body used in the present invention is preferably in the form of particles. If it is in the form of particles, it is preferable because it is possible to achieve both performance and economy. The fibrous inorganic porous body has an increased specific surface area, higher contact efficiency with the target gas, and better performance (removal efficiency), but is not effective in consideration of economy because of its high price.
　無機多孔質体の平均粒子径は、５０～１０００μｍの範囲が好ましい。無機多孔質体の平均粒子径が小さいほど、吸着剤のＶＯＣ（揮発性有機化合物）ガスの吸着速度は速くなるが、その一方で、無機多孔質体が飛散しやすく、無機多孔質体の取り扱い性や加工性が低下するため、無機多孔質体の平均粒子径は５０μｍ以上であることが好ましく、１００μｍ以上であることがより好ましい。また、無機多孔質体の平均粒子径が大きいと、無機多孔質体の製造が難しく、また強度的にも脆弱となる為、無機多孔質体が破壊されやすくなり、逆に粉塵が発生してしまう傾向にあるため、無機多孔質体の平均粒子径は１０００μｍ以下であることが好ましく、６００μｍ以下であることがより好ましい。ここでいう平均粒子径は、ＪＩＳ－Ｋ１４７４（２０１４）活性炭試験方法に規定された質量平均粒子径を指す。 The average particle size of the inorganic porous body is preferably in the range of 50 to 1000 μm. The smaller the average particle size of the inorganic porous body, the faster the adsorption rate of VOC (volatile organic compound) gas of the adsorbent, but on the other hand, the inorganic porous body easily scatters and the handling of the inorganic porous body is handled. The average particle size of the inorganic porous body is preferably 50 μm or more, more preferably 100 μm or more, because the property and processability are deteriorated. Further, if the average particle size of the inorganic porous body is large, it is difficult to manufacture the inorganic porous body and the strength is also fragile, so that the inorganic porous body is easily destroyed and dust is generated. The average particle size of the inorganic porous body is preferably 1000 μm or less, and more preferably 600 μm or less. The average particle size referred to here refers to the mass average particle size specified in the JIS-K1474 (2014) activated carbon test method.
　本発明に用いる無機多孔質体の平均細孔径としては、４０～５００オングストロームであることが好ましい。無機多孔質体の平均細孔径を５００オングストローム以下とすることで、無機多孔質体の機械的強度の低下を抑制しつつ無機多孔質体の比表面積を大きくすることができ、吸着剤の低沸点アルデヒドの除去性能がより優れたものとなる。上記の理由から、無機多孔質体の平均細孔径は３００オングストローム以下であることがより好ましい。また、無機多孔質体の平均細孔径を４０オングストローム以上とすることで、酸ヒドラジド類やＶＯＣガスの粒状無機多孔質体の細孔内部への進入を促進することができる。上記の理由から、無機多孔質体の平均細孔径は５０オングストローム以上であることが好ましい。 The average pore diameter of the inorganic porous material used in the present invention is preferably 40 to 500 angstroms. By setting the average pore diameter of the inorganic porous body to 500 angstroms or less, it is possible to increase the specific surface area of the inorganic porous body while suppressing a decrease in the mechanical strength of the inorganic porous body, and the low boiling point of the adsorbent. The aldehyde removal performance becomes better. For the above reasons, the average pore diameter of the inorganic porous body is more preferably 300 angstroms or less. Further, by setting the average pore diameter of the inorganic porous body to 40 angstroms or more, it is possible to promote the entry of acid hydrazides and VOC gas into the pores of the granular inorganic porous body. For the above reasons, the average pore size of the inorganic porous body is preferably 50 angstroms or more.
　次に本発明で採用する無機多孔質体の比表面積は、ＢＥＴ比表面積で３０～１０００ｍ２／ｇであることが好ましい。無機多孔質体の比表面積を３０ｍ２／ｇ以上とすることで、無機多孔質体が担持したアミン系化合物の反応場として実効的な面積が向上し、吸着剤と除去しようとするＶＯＣガスとの反応速度が向上する。上記の理由から、無機多孔質体のＢＥＴ比表面積は５０ｍ２／ｇ以上であることがより好ましい。また、無機多孔質体のＢＥＴ比表面積が１０００ｍ２／ｇ以下であることで、無機多孔質体の機械的強度の低下による取り扱い性の低下を抑制できるとともに、二次発臭につながるＶＯＣガスの吸着剤への非意図的吸着を抑制することが可能となる。 Next, the specific surface area of the inorganic porous body used in the present invention is preferably 30 to 1000 m 2 / g in terms of BET specific surface area. By setting the specific surface area of the inorganic porous body to 30 m 2 / g or more, the effective area as a reaction field of the amine compound supported by the inorganic porous body is improved, and the adsorbent and the VOC gas to be removed are used. Reaction speed is improved. For the above reasons, the BET specific surface area of the inorganic porous body is more preferably 50 m 2 / g or more. Further, when the BET specific surface area of the inorganic porous body is 1000 m 2 / g or less, it is possible to suppress a decrease in handleability due to a decrease in mechanical strength of the inorganic porous body, and a VOC gas leading to secondary odor can be suppressed. It is possible to suppress unintentional adsorption to the adsorbent.
　本発明に用いる無機多孔質体はＶＯＣガス中に含まれる低沸点アルデヒドを除去するためのアミン系化合物として酸ヒドラジド類を担持している。また、この酸ヒドラジド類は、無機多孔質体への担持加工のし易さの観点から、水溶性の酸ヒドラジド類であることが好ましい。 The inorganic porous body used in the present invention carries acid hydrazides as an amine compound for removing low boiling point aldehydes contained in VOC gas. Further, the acid hydrazides are preferably water-soluble acid hydrazides from the viewpoint of easy support processing on the inorganic porous body.
　ここで、水溶性の酸ヒドラジド類とは、水（２５℃）に対し、０．５質量％以上溶解する酸ヒドラジド類をいう。 Here, the water-soluble acid hydrazides refer to acid hydrazides that dissolve in 0.5% by mass or more with respect to water (25 ° C.).
　そして、酸ヒドラジド類は、カルボン酸とヒドラジンとから誘導される－ＣＯ－ＮＨＮＨ２で表される酸ヒドラジド基を有する化合物であり、ヒドラジド末端のα位に、更に非共有電子対を有する窒素原子が結合しており、これにより求核反応性が著しく向上している。この非共有電子対がアルデヒド化合物（アルデヒド化合物とは、低沸点アルデヒドおよび高沸点アルデヒドを含む概念である。）のカルボニル炭素原子を求核的に攻撃して反応し、アルデヒド化合物をヒドラジン誘導体として固定化することにより、アルデヒド化合物の吸着性能を発現できると考えられる。 Acid hydrazides are compounds having an acid hydrazide group represented by -CO-NHNH 2 derived from a carboxylic acid and hydrazine, and a nitrogen atom having an unshared electron pair at the α-position at the hydrazide terminal. Is bound, which significantly improves the nucleophilic reactivity. This unshared electron pair reacts by nucleophilically attacking the carbonyl carbon atom of an aldehyde compound (aldehyde compound is a concept including low boiling point aldehyde and high boiling point aldehyde), and fixes the aldehyde compound as a hydrazine derivative. It is considered that the adsorption performance of the aldehyde compound can be exhibited by the conversion.
　アルデヒド化合物の中でもアセトアルデヒドは、カルボニル炭素のα位に電子供与性のアルキル基を有するために、カルボニル炭素の求電子性が低く化学吸着されにくいが、本発明に用いるガス吸着剤において採用する酸ヒドラジド類は前述のとおり求核反応性が高いため、アセトアルデヒドに対しても良好な化学吸着性能を発現する。 Among the aldehyde compounds, acetaldehyde has an electron-donating alkyl group at the α-position of the carbonyl carbon, so that the electrophile of the carbonyl carbon is low and it is difficult to be chemically adsorbed. However, the acid hydrazide used in the gas adsorbent used in the present invention. As mentioned above, since the class has high electrophilic reactivity, it exhibits good chemisorption performance even for acetaldehyde.
　酸ヒドラジド類としては、例えば、カルボジヒドラジド、グルタミン酸ジヒドラジド、コハク酸ジヒドラジド、及びアジピン酸ジヒドラジドからなる群より選ばれる１種以上を含むものを挙げることができる。これらの中でも、とりわけアジピン酸ジヒドラジドがアルデヒド化合物の吸着性能に優れる点で好ましい。また、アルデヒド化合物の吸着性能を上げる目的でアジピン酸ジヒドラジドとコハク酸ジヒドラジドを併用することがより好ましい。 Examples of acid hydrazides include those containing one or more selected from the group consisting of carbodihydrazide, glutamic acid dihydrazide, succinic acid dihydrazide, and adipic acid dihydrazide. Among these, adipic acid dihydrazide is particularly preferable because it has excellent adsorption performance for aldehyde compounds. Further, it is more preferable to use adipic acid dihydrazide and succinic acid dihydrazide in combination for the purpose of improving the adsorption performance of the aldehyde compound.
　本発明で採用する酸ヒドラジド類の担持量は、無機多孔質体１００質量部に対して１～５０質量部であることが好ましい。酸ヒドラジド類の含有量を１質量部以上であることで、吸着剤のアルデヒド化合物の吸着性能をより向上させることができる。この理由から、酸ヒドラジド類の担持量は３質量部以上であることがより好ましい。そして、酸ヒドラジド類の担持量を５０質量部以下とすることで、無機多孔質体に担持された酸ヒドラジド類の結晶化を抑制することができ、結晶化した酸ヒドラジド類が無機多孔質体の細孔を閉塞することを抑制することができる。そして、このことにより、吸着剤のアルデヒド化合物の吸着性能を向上させることができるとともに、吸着剤を用いたエアフィルター用濾材からの酸ヒドラジド類の脱落も抑制することができる。 The amount of the acid hydrazides used in the present invention is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the inorganic porous body. When the content of acid hydrazides is 1 part by mass or more, the adsorption performance of the aldehyde compound of the adsorbent can be further improved. For this reason, the amount of acid hydrazides supported is more preferably 3 parts by mass or more. By setting the amount of the acid hydrazides carried to 50 parts by mass or less, the crystallization of the acid hydrazides carried on the inorganic porous body can be suppressed, and the crystallized acid hydrazides are the inorganic porous body. It is possible to suppress the blockage of the pores of Hydrazide. As a result, the adsorption performance of the aldehyde compound of the adsorbent can be improved, and the removal of acid hydrazides from the filter medium for the air filter using the adsorbent can be suppressed.
　次に、無機多孔質体への酸ヒドラジド類の担持処理法としては、所望の特性が得られる手法であれば特に制限されないが、例えば、酸ヒドラジド類を溶解させた水溶液中に無機多孔質体を投入・分散させることで、酸ヒドラジド類を無機多孔質体に担持させる方法や、酸ヒドラジド類を溶媒中に溶解させた水溶液を無機多孔質体に噴霧・塗布し、次に、この無機多孔質体を乾燥する方法などが挙げられる。また、上記の溶媒としては酸ヒドラジド類の特性ならびに作業性を考慮し適当なものを選択することができる。このうち安全性ならびに作業性の観点から水系溶媒を用いることが好ましく、溶媒として純水を用いることがより好ましい。 Next, the method for supporting the acid hydrazides on the inorganic porous body is not particularly limited as long as it is a method that can obtain desired characteristics. For example, the inorganic porous body is contained in an aqueous solution in which the acid hydrazides are dissolved. A method of supporting acid hydrazides on an inorganic porous body by adding and dispersing acid hydrazides, or an aqueous solution in which acid hydrazides are dissolved in a solvent is sprayed and applied to the inorganic porous body, and then this inorganic porous body is sprayed and applied. Examples include a method of drying the body. Further, as the above solvent, an appropriate solvent can be selected in consideration of the characteristics and workability of acid hydrazides. Of these, it is preferable to use an aqueous solvent from the viewpoint of safety and workability, and it is more preferable to use pure water as the solvent.
　本発明に用いる酸ヒドラジド類を担持する無機多孔質体は、２５℃の水１００ｇに５ｇ分散させた際のｐＨが３．０～７．５の範囲であることが好ましい。ｐＨが７．５以下であることで、酸ヒドラジド類の非共有電子対のアルデヒド化合物のカルボニル炭素原子への求核的攻撃による反応から生成した中間体が、酸性の反応場においてプロトン化されるため脱水し易くなり、前記中間体の誘導体への固定化反応が十分に進む。上記の理由からｐＨは６．５以下であることがより好ましい。また、ｐＨが３．０以上であることで、酸ヒドラジド類の非共有電子対がアルデヒド化合物のカルボニル炭素原子を求核的に攻撃する活性がより高いものとなり、吸着剤のアルデヒド化合物の吸着性能がより優れたものとなる。なおｐＨは、２５℃の純水に酸ヒドラジド類を担持した無機多孔質体が５質量％となるよう浸漬し、軽く攪拌した後１０分間放置し、液のｐＨをｐＨ計にて測定した値をいう。 The inorganic porous body carrying the acid hydrazides used in the present invention preferably has a pH in the range of 3.0 to 7.5 when 5 g is dispersed in 100 g of water at 25 ° C. When the pH is 7.5 or less, the intermediate produced from the reaction by the nucleophilic attack on the carbonyl carbon atom of the aldehyde compound of the unshared electron pair of acid hydrazides is protonated in the acidic reaction field. Therefore, it becomes easy to dehydrate, and the immobilization reaction of the intermediate to the derivative proceeds sufficiently. For the above reasons, the pH is more preferably 6.5 or less. In addition, when the pH is 3.0 or higher, the unshared electron pair of acid hydrazides becomes more active in nucleophilically attacking the carbonyl carbon atom of the aldehyde compound, and the adsorption performance of the aldehyde compound of the adsorbent becomes higher. Becomes better. The pH was measured by immersing the inorganic porous body carrying acid hydrazides in pure water at 25 ° C. so as to be 5% by mass, stirring lightly, and then leaving it for 10 minutes, and measuring the pH of the liquid with a pH meter. To say.
　酸ヒドラジド類を担持した無機多孔質体のｐＨは、有機酸を添加することにより調整することができる。有機酸としては、それ自体は臭気を発生しないものであり、かつ、吸湿性の低いものを採用することが好ましい。上記のような有機酸の具体的な例としては、アジピン酸、スルファニル酸、リンゴ酸、クエン酸等が挙げられ、用いる酸ヒドラジド類に応じて適宜選択すればよく、中でもアジピン酸を好ましく採用することができる。本発明では上記有機酸の代替として、酸性カチオン交換樹脂を用いる。酸性カチオン交換樹脂はそれ自体の臭気の発生や吸湿性の発現を伴わないため好ましい。 The pH of the inorganic porous body carrying acid hydrazides can be adjusted by adding an organic acid. As the organic acid, it is preferable to use an organic acid that does not generate an odor by itself and has low hygroscopicity. Specific examples of the organic acid as described above include adipic acid, sulfanic acid, malic acid, citric acid and the like, which may be appropriately selected according to the acid hydrazides used, and adipic acid is preferably adopted. be able to. In the present invention, an acidic cation exchange resin is used as an alternative to the organic acid. Acidic cation exchange resins are preferable because they do not generate their own odor or hygroscopicity.
　一方で酸ヒドラジド類はタバコ煙に多く含まれるアセトアルデヒドとの反応性に優れるため、タバコ独特の刺激臭を著しく緩和する効果を得ることができる。ヒドラジド化合物としては上述した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から任意に選択できる。中でもアジピン酸ジヒドラジドは、適度な溶解度を示し、吸着剤の微細孔への添着が容易であるためより好ましい。 On the other hand, acid hydrazides have excellent reactivity with acetaldehyde, which is abundant in tobacco smoke, so that the effect of significantly reducing the pungent odor peculiar to tobacco can be obtained. The hydrazide compound can be arbitrarily selected from the above-mentioned adipic acid dihydrazide, dodecanedioic acid dihydrazide, succinate dihydrazide and the like. Among them, adipic acid dihydrazide is more preferable because it exhibits an appropriate solubility and the adsorbent can be easily attached to the micropores.
　本発明の濾材には、極性、無極性ガスを問わず効率よく対象ガスを除去するために、不織布の層間に、アミン系化合物が担持された無機多孔質体の他にイオン交換樹脂を含んでいる。 The filter medium of the present invention contains an ion exchange resin in addition to an inorganic porous body in which an amine compound is supported between layers of the non-woven fabric in order to efficiently remove the target gas regardless of whether it is a polar or non-polar gas. There is.
　イオン交換樹脂としては、特に制限はなく、塩基性ガスを有効に化学吸着できる強酸性カチオン交換樹脂ないし弱酸性カチオン交換樹脂や、酸性ガスを有効に化学吸着できる強塩基性アニオン交換樹脂ないし弱塩基性アニオン交換樹脂のほか、両性のイオン交換樹脂等を用いることができる。 The ion exchange resin is not particularly limited, and is a strongly acidic cation exchange resin or a weakly acidic cation exchange resin capable of effectively chemically adsorbing a basic gas, or a strongly basic anion exchange resin or a weak base capable of effectively chemically adsorbing an acidic gas. In addition to the sex anion exchange resin, an amphoteric ion exchange resin or the like can be used.
　イオン交換樹脂の母体は、通常はスチレンとジビニルベンゼンの共重合体であり、その母体構造によって、透明でほぼ均質なゲル形と、物理的に大きな孔径をもったマクロポーラス形とに大別され、母体構造と各種交換基とを組み合わせることで多種のものがあるが、本発明では、いずれのイオン交換樹脂でも使用することができる。例えば交換基にスルホン酸基を用いた強酸性カチオン交換樹脂、交換基にカルボキシル基あるいはフェノール水酸基を用いた弱酸性カチオン交換樹脂、交換基に第四アンモニウム塩基を用いた強塩基性アニオン交換樹脂、交換基に第一、第二、第三アミンを用いた弱塩基性アニオン交換樹脂が挙げられる。中でもアンモニア等の塩基性臭気成分を吸着させるには、酸性カチオン交換樹脂を使用することがより好ましい。 The base of the ion exchange resin is usually a copolymer of styrene and divinylbenzene, and depending on its base structure, it is roughly divided into a transparent and almost homogeneous gel type and a macroporous type having a physically large pore size. , There are various types by combining the matrix structure and various exchange groups, but in the present invention, any ion exchange resin can be used. For example, a strongly acidic cation exchange resin using a sulfonic acid group as an exchange group, a weakly acidic cation exchange resin using a carboxyl group or a phenol hydroxyl group as an exchange group, and a strongly basic anion exchange resin using a quaternary ammonium base as an exchange group. Examples thereof include weakly basic anion exchange resins using first, second and third amines as exchange groups. Above all, in order to adsorb a basic odor component such as ammonia, it is more preferable to use an acidic cation exchange resin.
　また、本発明で用いる酸性カチオン交換樹脂は粒子状が好ましい。粒子状であれば、性能面と経済面の両立が可能であるため好ましい。繊維状の酸性カチオン交換樹脂では、比表面積が増加し対象ガスとの接触効率が高くなり性能面（除去効率）は良くなるが、高価格であるため経済面を考慮すると有効ではない。 Further, the acidic cation exchange resin used in the present invention is preferably in the form of particles. If it is in the form of particles, it is preferable because it is possible to achieve both performance and economy. The fibrous acidic cation exchange resin increases the specific surface area, increases the contact efficiency with the target gas, and improves the performance (removal efficiency), but it is not effective in consideration of economy because of its high price.
　さらに、本発明で用いる酸性カチオン交換樹脂の平均粒子径は１０００μｍ以下が好ましいが、酸性カチオン交換樹脂の平均粒子径が小さいほど、吸着剤のガスの吸着速度は速くなるため、２００μｍ以下がより好ましい。平均粒子径の下限は特に限定しないが、平均粒子径が１００μｍ未満になると粒子が飛散しやすく、酸性カチオン交換樹脂の取り扱い性や加工性が低下する傾向にあるため、酸性カチオン交換樹脂の平均粒子径は５０μｍ以上が好ましく、１００μｍ以上であることがより好ましい。ここでいう平均粒子径は、ＪＩＳ－Ｋ１４７４（２０１４）に規定された活性炭試験方法で測定された質量平均粒子径を指す。 Further, the average particle size of the acidic cation exchange resin used in the present invention is preferably 1000 μm or less, but the smaller the average particle size of the acidic cation exchange resin, the faster the adsorption rate of the adsorbent gas, and therefore 200 μm or less is more preferable. .. The lower limit of the average particle size is not particularly limited, but if the average particle size is less than 100 μm, the particles tend to scatter and the handleability and processability of the acid cation exchange resin tend to deteriorate. Therefore, the average particles of the acid cation exchange resin are average particles. The diameter is preferably 50 μm or more, and more preferably 100 μm or more. The average particle size referred to here refers to the mass average particle size measured by the activated carbon test method specified in JIS-K1474 (2014).
　本発明で用いる酸ヒドラジド類が担持された無機多孔質体に対する酸性カチオン交換樹脂の含有比率は１０～３００％範囲内であることが好ましい。酸性カチオン交換樹脂の含有比率を１０％以上とすることで、吸着剤のアンモニアの吸着性能をより向上させることができる。この理由から、酸性カチオン交換樹脂の含有比率は３０％以上であることがより好ましい。そして、酸性カチオン交換樹脂の含有比率を３００％以下とすることで、アンモニアとアルデヒドガスの双方をバランス良く効率的に除去することができる。本発明の濾材には、不織布の層間に、アミン系化合物が担持された無機多孔質体、イオン交換樹脂の他に、さらに活性炭を含むことが好ましい。活性炭としては、ヤシ殻、石炭、木粉、フェノール樹脂等を原料とするものが好ましい。特に、焼成、洗浄、粉砕、分球などの工程を経て製品化される比較的粒度の小さい粒状活性炭が好ましい。 The content ratio of the acidic cation exchange resin to the inorganic porous body carrying the acid hydrazides used in the present invention is preferably in the range of 10 to 300%. By setting the content ratio of the acidic cation exchange resin to 10% or more, the adsorption performance of ammonia as an adsorbent can be further improved. For this reason, the content ratio of the acidic cation exchange resin is more preferably 30% or more. By setting the content ratio of the acidic cation exchange resin to 300% or less, both ammonia and aldehyde gas can be efficiently removed in a well-balanced manner. The filter medium of the present invention preferably contains activated carbon in addition to the inorganic porous body in which the amine compound is supported and the ion exchange resin between the layers of the non-woven fabric. As the activated carbon, those made from coconut shell, coal, wood flour, phenol resin and the like are preferable. In particular, granular activated carbon having a relatively small particle size, which is commercialized through steps such as firing, washing, pulverization, and spheroidization, is preferable.
　また本発明の濾材に使用する活性炭は、以下の細孔構造を有するものであることが好ましい。すなわち、ＭＰ法により算出される細孔径が０．４ｎｍ以上、２ｎｍ以下である細孔の細孔容積が０．４０ｃｃ／ｇ以上、０．５５ｃｃ／ｇ以下の範囲であり、かつ、ＭＰ法およびＢＪＨ法により算出される細孔径が０．４ｎｍ以上の細孔の細孔容積に対する、活性炭の細孔径が０．４ｎｍ以上、２ｎｍ以下である細孔の細孔容積の比率が７５％以上であることが好ましい。より好ましい容積の比率は８５％以上である。 The activated carbon used in the filter medium of the present invention preferably has the following pore structure. That is, the pore volume of the pores having a pore diameter of 0.4 nm or more and 2 nm or less calculated by the MP method is in the range of 0.40 cc / g or more and 0.55 cc / g or less, and the MP method and The ratio of the pore volume of the pores having a pore diameter of 0.4 nm or more and 2 nm or less to the pore volume of the pores having a pore diameter of 0.4 nm or more calculated by the BJH method is 75% or more. Is preferable. A more preferable volume ratio is 85% 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が形成する細孔容積が特定の範囲であり、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、０．４ｎｍ以上の細孔の細孔容積に対する、細孔径が０．４ｎｍ以上、２ｎｍ以下の細孔の細孔容積の比率が７５％以上であること、すなわち、細孔径が２ｎｍを超える細孔の細孔容積の合計の細孔径が０．４ｎｍ以上の細孔の細孔容積に対する比率が２５％未満であることで、この活性炭を有する吸着剤は、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 is in a specific range, that is, a specific number of pores of a specific size are present in the activated carbon, and further. , The ratio of the pore volume of pores having a pore diameter of 0.4 nm or more and 2 nm or less to the pore volume of pores of 0.4 nm or more is 75% or more, that is, the pore diameter is finer than 2 nm. Since the ratio of the total pore volume of the pores to the pore volume of the pores having a pore diameter of 0.4 nm or more is less than 25%, the adsorbent having this activated carbon can adsorb and remove odorous components such as toluene. It has excellent performance, and the desorption of odorous components such as toluene once adsorbed from the adsorbent is suppressed.
　ＭＰ（ＭＩＣＲＯＰＯＲＥ）法は活性炭が備える微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。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）法などがあるが、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、この範囲の解析に適しているＭＰ法を採用する。また、活性炭が備える細孔のうち、細孔径が２ｎｍを超えるマクロ孔の解析にはＢＪＨ法を採用する。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細孔径が０．４ｎｍ以上の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の値をいう。 The MP (MICROPORE) method is an analysis method that can quantify the distribution of micropores in the pore size of activated carbon. Generally, as a method for analyzing the pore diameter and pore volume of the pore diameter of activated carbon, there are MP (MICROPORE) method, BJH (Barrett-Joiner-Halenda) method, and the like. Among them, the MP method suitable for analysis in this range is adopted for the analysis of micropores having a pore diameter of 0.4 to 2 nm in which capillary condensation does not occur. Further, among the pores provided in activated carbon, the BJH method is adopted for the analysis of macropores having a pore diameter exceeding 2 nm. Here, the pore volume of the pore having a pore diameter of 0.4 nm or more calculated by the MP method and the BJH method in the present invention is obtained by the value of the pore volume obtained by the MP method and the BJH method. It means the total value of the pore volume values.
　また、活性炭にはアルカリ金属化合物を添着することが好ましい。アルカリ金属化合物は、酢酸などの酸系ガスとの反応性が高く、酸系の「すっぱい臭気」を緩和し、使用者が感知しにくい臭気に変化させられる。アルカリ金属化合物としては水酸化カリウム、炭酸カリウム、炭酸水素ナトリウムなどから任意に選択できる。本願では、アルカリ金属化合物を添着した活性炭を、アルカリ添着活性炭と称する。 Further, it is preferable to impregnate the activated carbon with an alkali metal compound. Alkali metal compounds have high reactivity with acid-based gases such as acetic acid, alleviate the acid-based "sour odor", and can change the odor that is difficult for the user to perceive. The alkali metal compound can be arbitrarily selected from potassium hydroxide, potassium carbonate, sodium hydrogen carbonate and the like. In the present application, activated carbon impregnated with an alkali metal compound is referred to as alkaline impregnated activated carbon.
　不織布を３枚以上積層する場合は、活性炭、酸ヒドラジド類を担持した無機多孔質体及びカチオン交換樹脂は同層でも異層でもどの様な配置でも良いが、アルカリ添着をした活性炭を含む場合は、活性炭および無機多孔質体に添着している薬剤が互いに影響を受けない様にするために、アルカリ添着活性炭と酸ヒドラジド類を担持した無機多孔質体は異層に配置することが望ましい。本発明では、上述した吸着剤を不織布の層間に担持する。その際の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。 When three or more non-woven fabrics are laminated, the activated carbon, the inorganic porous body carrying acid hydrazides, and the cation exchange resin may be arranged in any arrangement, either in the same layer or in different layers, but when the activated carbon impregnated with alkali is contained. In order to prevent the chemicals adhering to the activated carbon and the inorganic porous body from being affected by each other, it is desirable to arrange the alkaline impregnated activated carbon and the inorganic porous body carrying the acid hydrazides in different layers. In the present invention, the above-mentioned adsorbent is supported between layers of the non-woven fabric. The form of the non-woven fabric at that time is not particularly limited, and examples thereof include chemical-bonded non-woven fabrics, wet paper-made non-woven fabrics, spunbonded non-woven fabrics, melt-blown non-woven fabrics, spunlaced non-woven fabrics, and air-laid non-woven fabrics.
　吸着剤の不織布へ担持させる方法（濾材作製方法）としては、粒子状の吸着剤を、この吸着剤と同等の粒子サイズを有する熱接着材料と均一に混合したものを不織布の一方の平面上に均一に散布し、加熱して接着材料を溶融させる方法がある。その際用いられる熱接着性材料は、ポリエステル樹脂、ポリアミド樹脂、ポリオレフィン樹脂、およびこれらの変成樹脂等の熱可塑性樹脂からなる繊維、粒子、粉末のようなものである。 As a method of supporting the adsorbent on the non-woven fabric (filter medium manufacturing method), a particulate adsorbent uniformly mixed with a heat-adhesive material having a particle size equivalent to that of the adsorbent is uniformly mixed on one flat surface of the non-woven fabric. There is a method of spraying evenly and heating to melt the adhesive material. The heat-adhesive material used at that time is such as fibers, particles, and powder made of a thermoplastic resin such as a polyester resin, a polyamide resin, a polyolefin resin, and a modified resin thereof.
　以下、本発明を実施例に基づいてさらに具体的に説明する。なお、本発明は下記実施例に限定して解釈されるものではない。
［測定方法］
　（１）ＭＰ法及びＢＪＨ法による活性炭の細孔容積の測定
　測定装置として日本ベル製 ＢＥＬＳＯＲＰ１８ＰＬＵＳ-ＨＴを用いて、活性炭０．１ｇをガラスセルに入れ、１５０℃で５時間減圧脱気した後、窒素ガス吸着法により細孔径分布解析を実施し、細孔径分布比率と細孔容積を算出した。細孔容積と細孔径分布比率を掛け合わせ、細孔径が０．４ｎｍ以上、２ｎｍ以下の細孔の細孔容積を算出した。具体的には、細孔径が０．４ｎｍ以上、２ｎｍ以下の細孔の細孔容積はＭＰ法により求めた。細孔径が０．４ｎｍ以上の細孔容積については、細孔径が２ｎｍを超える細孔の細孔容積をＢＪＨ法により算出し、この容積と前述のＭＰ法で求めた細孔径が０．４ｎｍ以上、２ｎｍ以下の細孔容積を足したものとした。 Hereinafter, the present invention will be described in more detail based on examples. The present invention is not construed as being limited to the following examples.
[Measuring method]
(1) Measurement of pore volume of activated carbon by MP method and BJH method Using BELSORP18PLUS-HT manufactured by Nippon Bell as a measuring device, 0.1 g of activated carbon was placed in a glass cell, degassed under reduced pressure at 150 ° C. for 5 hours, and then degassed. The pore size distribution was analyzed by the nitrogen gas adsorption method, and the pore size distribution ratio and the pore volume were calculated. By multiplying the pore volume and the pore diameter distribution ratio, the pore volume of pores having a pore diameter of 0.4 nm or more and 2 nm or less was calculated. Specifically, the pore volume of pores having a pore diameter of 0.4 nm or more and 2 nm or less was determined by the MP method. For the pore volume having a pore diameter of 0.4 nm or more, the pore volume of the pore having a pore diameter exceeding 2 nm is calculated by the BJH method, and this volume and the pore diameter obtained by the above-mentioned MP method are 0.4 nm or more. The pore volume of 2 nm or less was added.
　（２）ＭＰ法およびＢＪＨ法により算出される細孔径が０．４ｎｍ以上の細孔の細孔容積に対する、細孔径が０．４ｎｍ以上、２ｎｍ以下の細孔の細孔容積の比率は以下の式より求めた。
計算式：｛細孔径が０．４ｎｍ以上、２ｎｍ以下の細孔の細孔容積（ｃｃ／ｇ）／細孔径が０．４ｎｍ以上の細孔の細孔容積（ｃｃ／ｇ）}×１００（％）。 (2) The ratio of the pore volume of the pores having a pore diameter of 0.4 nm or more and 2 nm or less to the pore volume of the pores having a pore diameter of 0.4 nm or more calculated by the MP method and the BJH method is as follows. Obtained from the formula.
Calculation formula: {Pore volume of pores with a pore diameter of 0.4 nm or more and 2 nm or less (cc / g) / Pore volume of pores with a pore diameter of 0.4 nm or more (cc / g)} × 100 ( %).
　（３）脱臭性能評価
　アンモニア、アセトアルデヒド、酢酸の脱臭性能評価の方法を以下に、脱臭性能の評価基準を表２に示す。 (3) Evaluation of deodorizing performance The method for evaluating the deodorizing performance of ammonia, acetaldehyde, and acetic acid is shown below, and the evaluation criteria for deodorizing performance are shown in Table 2.
　（４－１）アンモニアの脱臭性能評価
　平板状の濾材を実験用のダクトに取り付け、空気を０．２ｍ／ｓｅｃの速度で送風した。さらに上流側から、標準ガスボンベによりアンモニアを上流濃度３０ｖｏｌｐｐｍとなるように添加し、繊維シートの上流側と下流側とにおいてエアをサンプリングし、赤外吸光式連続モニターを使用してそれぞれのアンモニア濃度を経時的に測定した。
アンモニアの除去効率は以下の式により算出した。
＜算出式＞
　除去効率（％）＝（上流側濃度－下流側濃度）／上流側濃度×１００。 (4-1) Evaluation of Ammonia Deodorizing Performance A flat plate-shaped filter medium was attached to the experimental duct, and air was blown at a speed of 0.2 m / sec. Further, from the upstream side, ammonia was added to an upstream concentration of 30 volppm using a standard gas cylinder, air was sampled on the upstream side and the downstream side of the fiber sheet, and the respective ammonia concentrations were measured using an infrared absorption continuous monitor. Measured over time.
The removal efficiency of ammonia was calculated by the following formula.
<Calculation formula>
Removal efficiency (%) = (upstream concentration-downstream concentration) / upstream concentration x 100.
　（４－２）アセトアルデヒドの脱臭性能評価
　平板状の濾材を実験用のダクトに取り付け、空気を０．２ｍ／ｓｅｃの速度で送風した。さらに上流側から、標準ガスボンベによりアセトアルデヒドを上流濃度１０ｖｏｌｐｐｍとなるように添加し、繊維シートの上流側と下流側とにおいてエアをサンプリングし、赤外吸光式連続モニターを使用してそれぞれのアセトアルデヒド濃度を経時的に測定した。
アセトアルデヒドの除去効率は以下の式により算出した。
＜算出式＞
　除去効率（％）＝（上流側濃度－下流側濃度）／上流側濃度×１００。 (4-2) Evaluation of deodorizing performance of acetaldehyde A flat plate-shaped filter medium was attached to an experimental duct, and air was blown at a speed of 0.2 m / sec. Further, from the upstream side, acetaldehyde was added to an upstream concentration of 10 volppm using a standard gas cylinder, air was sampled on the upstream side and the downstream side of the fiber sheet, and the respective acetaldehyde concentrations were measured using an infrared absorption continuous monitor. Measured over time.
The removal efficiency of acetaldehyde was calculated by the following formula.
<Calculation formula>
Removal efficiency (%) = (upstream concentration-downstream concentration) / upstream concentration x 100.
　（４－３）酢酸の脱臭性能評価
　平板状の濾材を実験用のダクトに取り付け、空気を０．２ｍ／ｓｅｃの速度で送風した。さらに上流側から、標準ガスボンベにより酢酸を上流濃度８０ｖｏｌｐｐｍとなるように添加し、繊維シートの上流側と下流側とにおいてエアをサンプリングし、赤外吸光式連続モニターを使用してそれぞれの酢酸濃度を経時的に測定した。
酢酸の除去効率は以下の式により算出した。
＜算出式＞
　除去効率（％）＝（上流側濃度－下流側濃度）／上流側濃度×１００。 (4-3) Evaluation of deodorizing performance of acetic acid A flat plate-shaped filter medium was attached to an experimental duct, and air was blown at a speed of 0.2 m / sec. Further, from the upstream side, acetic acid was added to an upstream concentration of 80 volppm using a standard gas cylinder, air was sampled on the upstream side and the downstream side of the fiber sheet, and the respective acetic acid concentrations were measured using an infrared absorption continuous monitor. Measured over time.
The acetic acid removal efficiency was calculated by the following formula.
<Calculation formula>
Removal efficiency (%) = (upstream concentration-downstream concentration) / upstream concentration x 100.
　（５）二次発臭試験（二次発臭（点）および快不快度（点））
　上記濾材の作製方法で得られた間口寸法２０ｃｍ×２０ｃｍの評価用濾材を容積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、燃焼煙を濾材に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。 (5) Secondary odor test (secondary odor (points) and comfort / discomfort (points))
The evaluation filter medium frontage dimensions 20 cm × 20 cm obtained by the above-mentioned method of manufacturing the filter medium was placed in a test chamber made of clear acrylic volume 1 m 3, by burning tobacco (Moebius 10 mg) 5 present in the test chamber, the combustion fumes Was collected on a filter medium for 30 minutes. This work was repeated 10 times to collect a total of 50 cigarette smokes.
　上記タバコ燃焼煙捕集後の評価用濾材を、寸法：２００×２８０ｍｍ、 厚み：０．０４ｍｍのチェック付きポリ袋に入れ、更にその袋内に１Lのクリーンエアーを入れた。その後、ポリ袋のチェックを閉じ、袋内を密閉状態として６時間静置した。 The evaluation filter medium after collecting the tobacco combustion smoke was placed in a checked plastic bag having dimensions: 200 x 280 mm and a thickness of 0.04 mm, and 1 L of clean air was further put into the bag. After that, the check of the plastic bag was closed, and the inside of the bag was kept in a sealed state for 6 hours.
　上記調整したポリ袋内から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。 The odor intensity and the degree of comfort and discomfort of the air discharged from the adjusted plastic bag were scored by five panelists according to the criteria shown in Tables 3 and 4, and the average value was calculated.
　［実施例１］
（無機多孔質体）
　無機多孔質体として、平均粒子径３００μｍの多孔質シリカ（富士シリシア化学（株））を用いた。
（接着材）
　接着剤として、低密度ポリエチレン（東京インキ（株））を用いた。（融点９８-１０４度）
(アミン系化合物)
　アミン系化合物として、アジピン酸ジヒドラジド(日本化成（株））を用いた。
(アルデヒド吸着剤）
　上記アジピン酸ジヒドラジドを７質量％水に溶解させた水溶液と無機多孔質体とを混合し乾燥させて、アルデヒド吸着剤を調整した。
（イオン交換樹脂）
　イオン交換樹脂としては、平均粒子径約１５０μｍの強酸性カチオン交換樹脂を用いた。
（活性炭）
　活性炭として、平均粒子径２３０μｍの炭酸水素ナトリウム添着活性炭を用いた。炭酸水素ナトリウム添着活性炭の製造条件は以下のとおりである。
（炭酸水素ナトリウム）
　炭酸水素ナトリウムとして、和光一級（富士フイルム和光純薬(株)）を用いた。
（炭酸水素ナトリウム添着活性炭）
　上記炭酸水素ナトリウムを７質量％水に溶解させた水溶液と後述する未添着活性炭Ａとを混合し乾燥させて、炭酸水素ナトリウム添着活性炭を調整した。
（未添着活性炭Ａ）
　未添着活性炭Ａとして、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０．４２ｃｃ／ｇ、ＭＰ法およびＢＪＨ法により算出される細孔径が０．４ｎｍ以上の細孔の細孔容積に対する、細孔径が０．４～２ｎｍの細孔の細孔容積の比率が８６％のものを用いた。
（不織布Ａ）
　不織布Ａとして、湿式抄紙不織布を用いた。
（不織布Ｂ）
　不織布Ｂとして、メルトブロー不織布を用いた。
（濾材の製造方法）
　濾材は以下製造方法により作成した。 [Example 1]
(Inorganic porous body)
As the inorganic porous body, porous silica (Fuji Silysia Chemical Ltd.) having an average particle diameter of 300 μm was used.
(Adhesive)
Low-density polyethylene (Tokyo Ink Co., Ltd.) was used as the adhesive. (Melting point 98-104 degrees)
(Amine compound)
Adipic acid dihydrazide (Nippon Kasei Chemical Company Limited) was used as the amine compound.
(Aldehyde adsorbent)
An aqueous solution prepared by dissolving the above-mentioned adipic acid dihydrazide in 7% by mass of water and an inorganic porous body were mixed and dried to prepare an aldehyde adsorbent.
(Ion exchange resin)
As the ion exchange resin, a strongly acidic cation exchange resin having an average particle diameter of about 150 μm was used.
(Activated carbon)
As the activated carbon, sodium hydrogen carbonate-impregnated activated carbon having an average particle size of 230 μm was used. The production conditions for the activated carbon impregnated with sodium hydrogen carbonate are as follows.
(sodium hydrogen carbonate)
Wako First Class (Fuji Film Wako Pure Chemical Industries, Ltd.) was used as sodium hydrogen carbonate.
(Activated carbon with sodium hydrogen carbonate)
An aqueous solution prepared by dissolving the sodium hydrogen carbonate in 7% by mass of water and an unimpregnated activated charcoal A described later were mixed and dried to prepare a sodium hydrogen carbonate impregnated activated charcoal.
(Unattached activated carbon A)
As the unattached activated carbon A, the pore volume of the pores having a pore diameter of 0.4 to 2 nm calculated by the MP method is 0.42 cc / g, and the pore diameter calculated by the MP method and the BJH method is 0.4 nm or more. The ratio of the pore volume of the pores having a pore diameter of 0.4 to 2 nm to the pore volume of the pores was 86%.
(Non-woven fabric A)
As the non-woven fabric A, a wet papermaking non-woven fabric was used.
(Non-woven fabric B)
As the non-woven fabric B, a melt-blown non-woven fabric was used.
(Manufacturing method of filter media)
The filter medium was prepared by the following manufacturing method.
　アルデヒド吸着剤１００質量部、接着剤９０質量部、イオン交換樹脂１００質量部および炭酸水素ナトリウム添着活性炭１００質量部をブレンドし、それを不織布Ａ上に均一に散布し、加熱炉内で１１０℃～１３０℃で加熱することにより接着剤を溶融させた。その散布面に不織布Ｂを積層後、ニップロールによって加圧し、濾材を製造した。 A blend of 100 parts by mass of an aldehyde adsorbent, 90 parts by mass of an adhesive, 100 parts by mass of an ion exchange resin and 100 parts by mass of activated carbon impregnated with sodium hydrogen carbonate is uniformly sprayed on the non-woven fabric A, and the temperature is increased from 110 ° C. in a heating furnace. The adhesive was melted by heating at 130 ° C. After laminating the non-woven fabric B on the sprayed surface, the non-woven fabric B was pressed by a nip roll to produce a filter medium.
　［実施例２］
（アルデヒド吸着剤）
　実施例１と同じものを用いた。
（接着剤）
　実施例１と同じものを用いた。
（イオン交換樹脂）
　実施例１と同じものを用いた。
（活性炭）
　実施例１と同じものを用いた。
（不織布Ａ）
　実施例１と同じものを用いた。
（不織布Ｂ）
　実施例１と同じものを用いた。
（不織布Ｃ）
　不織布Ｃとして、メルトブロー不織布を用いた。
（濾材の製造方法）
　濾材は以下製造方法により作成した。
アルデヒド吸着剤１００質量部とイオン交換樹脂１００質量部および接着剤６０質量部をブレンドし、それを不織布Ａ上に均一に散布し、加熱炉内で１１０℃～１３０℃で加熱することにより接着剤を溶融させ、その散布面に不織布Ｂを積層後、ニップロールによって加圧し、濾材を製造した。 [Example 2]
(Aldehyde adsorbent)
The same as in Example 1 was used.
(glue)
The same as in Example 1 was used.
(Ion exchange resin)
The same as in Example 1 was used.
(Activated carbon)
The same as in Example 1 was used.
(Non-woven fabric A)
The same as in Example 1 was used.
(Non-woven fabric B)
The same as in Example 1 was used.
(Non-woven fabric C)
As the non-woven fabric C, a melt-blown non-woven fabric was used.
(Manufacturing method of filter media)
The filter medium was prepared by the following manufacturing method.
100 parts by mass of aldehyde adsorbent, 100 parts by mass of ion exchange resin and 60 parts by mass of adhesive are blended, and the adhesive is uniformly sprayed on the non-woven fabric A and heated at 110 ° C to 130 ° C in a heating furnace. Was melted, the non-woven fabric B was laminated on the spraying surface, and then pressed by a nip roll to produce a filter medium.
　その後、その濾材の上に炭酸水素ナトリウム添着活性炭１００質量部と接着剤３０質量部を均一に散布し、加熱炉内で１１０℃～１３０℃で加熱することにより接着剤を溶融させ、その散布面に不織布Ｃを積層後、ニップロールによって加圧し、濾材を製造した。 Then, 100 parts by mass of activated carbon impregnated with sodium hydrogen carbonate and 30 parts by mass of adhesive are uniformly sprayed on the filter medium, and the adhesive is melted by heating in a heating furnace at 110 ° C. to 130 ° C., and the sprayed surface thereof. After laminating the non-woven fabric C on the surface, pressure was applied by a nip roll to produce a filter medium.
　［実施例３］
（アルデヒド吸着剤）
　実施例１と同じものを用いた。
（接着剤）
　実施例１と同じものを用いた。
（イオン交換樹脂）
　実施例１と同じものを用いた。
（活性炭）
　活性炭として、未添着活性炭Ａ（平均粒子径２３０μｍ）を用いた。
（不織布Ａ）
　実施例１と同じものを用いた。
（不織布Ｂ）
　実施例１と同じものを用いた。
（濾材）
　濾材の構成については下記条件のものを用いた。
条件：不織布Ａと不織布Ｂの層間にアルデヒド吸着剤１００質量部、接着剤９０質量部、イオン交換樹脂１００質量部および未添着活性炭Ａ１００質量部を介在させた濾材。 [Example 3]
(Aldehyde adsorbent)
The same as in Example 1 was used.
(glue)
The same as in Example 1 was used.
(Ion exchange resin)
The same as in Example 1 was used.
(Activated carbon)
As the activated carbon, unimpregnated activated carbon A (average particle size 230 μm) was used.
(Non-woven fabric A)
The same as in Example 1 was used.
(Non-woven fabric B)
The same as in Example 1 was used.
(Filter material)
As for the composition of the filter medium, the one under the following conditions was used.
Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 90 parts by mass of an adhesive, 100 parts by mass of an ion exchange resin and 100 parts by mass of unattached activated carbon A are interposed between the nonwoven fabric A and the nonwoven fabric B.
　［実施例４］
（アルデヒド吸着剤）
　実施例１と同じものを用いた。
（接着剤）
　実施例１と同じものを用いた。
（イオン交換樹脂）
　実施例１と同じものを用いた。
（活性炭）
　活性炭として、未添着活性炭Ｂ（平均粒子径２３０μｍ、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０．３９ｃｃ／ｇ、ＭＰ法およびＢＪＨ法により算出される細孔径が０．４ｎｍ以上の細孔の細孔容積に対する、細孔径が０．４～２ｎｍの細孔の細孔容積の比率が７５％のもの）を用いた。
（不織布Ａ）
　実施例１と同じものを用いた。
（不織布Ｂ）
　実施例１と同じものを用いた。
（濾材）
　濾材の構成については下記条件のものを用いた。
条件：不織布Ａと不織布Ｂの層間にアルデヒド吸着剤１００質量部、接着剤９０質量部、イオン交換樹脂１００質量部および未添着活性炭Ｂ１００質量部を介在させた濾材。 [Example 4]
(Aldehyde adsorbent)
The same as in Example 1 was used.
(glue)
The same as in Example 1 was used.
(Ion exchange resin)
The same as in Example 1 was used.
(Activated carbon)
As the activated carbon, unattached activated carbon B (average particle size 230 μm, pore volume of pores having a pore diameter of 0.4 to 2 nm calculated by the MP method is 0.39 cc / g, calculated by the MP method and the BJH method). The ratio of the pore volume of the pores having a pore diameter of 0.4 to 2 nm to the pore volume of the pores having a pore diameter of 0.4 nm or more was 75%) was used.
(Non-woven fabric A)
The same as in Example 1 was used.
(Non-woven fabric B)
The same as in Example 1 was used.
(Filter material)
As for the composition of the filter medium, the one under the following conditions was used.
Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 90 parts by mass of an adhesive, 100 parts by mass of an ion exchange resin and 100 parts by mass of unattached activated carbon B are interposed between the nonwoven fabric A and the nonwoven fabric B.
　［実施例５］
（アルデヒド吸着剤）
　実施例１と同じものを用いた。
（接着剤）
　実施例１と同じものを用いた。
（イオン交換樹脂）
　実施例１と同じものを用いた。
（活性炭）
　活性炭として、未添着活性炭Ｃ（平均粒子径２３０μｍ、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０．４０ｃｃ／ｇ、ＭＰ法およびＢＪＨ法により算出される細孔径が０．４ｎｍ以上の細孔の細孔容積に対する、細孔径が０．４～２ｎｍの細孔の細孔容積の比率が５１％のもの）を用いた。
（不織布Ａ）
　実施例１と同じものを用いた。
（不織布Ｂ）
　実施例１と同じものを用いた。
（濾材）
　濾材の構成については下記条件のものを用いた。
条件：不織布Ａと不織布Ｂの層間にアルデヒド吸着剤１００質量部、接着剤９０質量部、イオン交換樹脂１００質量部および未添着活性炭Ｃ１００質量部を介在させた濾材。 [Example 5]
(Aldehyde adsorbent)
The same as in Example 1 was used.
(glue)
The same as in Example 1 was used.
(Ion exchange resin)
The same as in Example 1 was used.
(Activated carbon)
As the activated carbon, unattached activated carbon C (average particle size 230 μm, pore volume of pores having a pore diameter of 0.4 to 2 nm calculated by the MP method is 0.40 cc / g, calculated by the MP method and the BJH method). The ratio of the pore volume of the pores having a pore diameter of 0.4 to 2 nm to the pore volume of the pores having a pore diameter of 0.4 nm or more was 51%) was used.
(Non-woven fabric A)
The same as in Example 1 was used.
(Non-woven fabric B)
The same as in Example 1 was used.
(Filter material)
As for the composition of the filter medium, the one under the following conditions was used.
Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 90 parts by mass of an adhesive, 100 parts by mass of an ion exchange resin and 100 parts by mass of unattached activated carbon C are interposed between the nonwoven fabric A and the nonwoven fabric B.
　［実施例６］
（アルデヒド吸着剤）
　実施例１と同じものを用いた。
（接着剤）
　実施例１と同じものを用いた。
（イオン交換樹脂）
　イオン交換樹脂としては、平均粒子径約６５０μｍの強酸性カチオン交換樹脂を用いた。
（炭酸水素ナトリウム添着活性炭）
　実施例１と同じものを用いた。
（不織布Ａ）
　実施例１と同じものを用いた。
（不織布Ｂ）
　実施例１と同じものを用いた。
（濾材）
　濾材の構成については下記条件のものを用いた。
条件：不織布Ａと不織布Ｂの層間にアルデヒド吸着剤１００質量部、接着剤９０質量部、イオン交換樹脂１００質量部および炭酸水素ナトリウム添着活性炭１００質量部を介在させた濾材。 [Example 6]
(Aldehyde adsorbent)
The same as in Example 1 was used.
(glue)
The same as in Example 1 was used.
(Ion exchange resin)
As the ion exchange resin, a strongly acidic cation exchange resin having an average particle diameter of about 650 μm was used.
(Activated carbon with sodium hydrogen carbonate)
The same as in Example 1 was used.
(Non-woven fabric A)
The same as in Example 1 was used.
(Non-woven fabric B)
The same as in Example 1 was used.
(Filter material)
As for the composition of the filter medium, the one under the following conditions was used.
Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 90 parts by mass of an adhesive, 100 parts by mass of an ion exchange resin and 100 parts by mass of activated carbon impregnated with sodium hydrogen carbonate are interposed between the nonwoven fabric A and the nonwoven fabric B.
　［実施例７］
（アルデヒド吸着剤）
　実施例１と同じものを用いた。
（接着剤）
　実施例１で用いたのと同様のものを用いた。
（イオン交換樹脂）
　実施例６と同じものを用いた。
（活性炭）
　実施例３と同じものを用いた。
（不織布Ａ）
　実施例１と同じものを用いた。
（不織布Ｂ）
　実施例１と同じものを用いた。
（濾材）
　濾材の構成については下記条件のものを用いた。
条件：不織布Ａと不織布Ｂの層間にアルデヒド吸着剤１００質量部、接着剤９０質量部、イオン交換樹脂１００質量部および未添着活性炭Ａ１００質量部を介在させた濾材。 [Example 7]
(Aldehyde adsorbent)
The same as in Example 1 was used.
(glue)
The same one used in Example 1 was used.
(Ion exchange resin)
The same as in Example 6 was used.
(Activated carbon)
The same as in Example 3 was used.
(Non-woven fabric A)
The same as in Example 1 was used.
(Non-woven fabric B)
The same as in Example 1 was used.
(Filter material)
As for the composition of the filter medium, the one under the following conditions was used.
Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 90 parts by mass of an adhesive, 100 parts by mass of an ion exchange resin and 100 parts by mass of unattached activated carbon A are interposed between the nonwoven fabric A and the nonwoven fabric B.
　［実施例８］
（アルデヒド吸着剤）
　実施例１と同じものを用いた。
（接着剤）
　実施例１と同じものを用いた。
（イオン交換樹脂）
　実施例６と同じものを用いた。
（不織布Ａ）
　実施例１と同じものを用いた。
（不織布Ｂ）
　実施例１と同じものを用いた。
（濾材）
　濾材の構成については下記条件のものを用いた。
条件：不織布Ａと不織布Ｂの層間にアルデヒド吸着剤１００質量部、接着剤６０質量部およびイオン交換樹脂１００質量部を介在させた濾材。 [Example 8]
(Aldehyde adsorbent)
The same as in Example 1 was used.
(glue)
The same as in Example 1 was used.
(Ion exchange resin)
The same as in Example 6 was used.
(Non-woven fabric A)
The same as in Example 1 was used.
(Non-woven fabric B)
The same as in Example 1 was used.
(Filter material)
As for the composition of the filter medium, the one under the following conditions was used.
Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 60 parts by mass of an adhesive and 100 parts by mass of an ion exchange resin are interposed between the layers of the non-woven fabric A and the non-woven fabric B.
　［実施例９］
（アルデヒド吸着剤）
　実施例１と同じものを用いた。
（接着剤）
　実施例１と同じものを用いた。
（イオン交換樹脂）
　実施例１と同じものを用いた。
（不織布Ａ）
　実施例１と同じものを用いた。
（不織布Ｂ）
　実施例１と同じものを用いた。
（濾材）
　濾材の構成については下記条件のものを用いた。
条件：不織布Ａと不織布Ｂの層間にアルデヒド吸着剤１００質量部、接着剤６０質量部およびイオン交換樹脂１００質量部を介在させた濾材。 [Example 9]
(Aldehyde adsorbent)
The same as in Example 1 was used.
(glue)
The same as in Example 1 was used.
(Ion exchange resin)
The same as in Example 1 was used.
(Non-woven fabric A)
The same as in Example 1 was used.
(Non-woven fabric B)
The same as in Example 1 was used.
(Filter material)
As for the composition of the filter medium, the one under the following conditions was used.
Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 60 parts by mass of an adhesive and 100 parts by mass of an ion exchange resin are interposed between the layers of the non-woven fabric A and the non-woven fabric B.
　［実施例１０］
（アルデヒド吸着剤）
　実施例１と同じものを用いた。
（接着剤）
　実施例１と同じものを用いた。
（イオン交換樹脂）
　実施例１と同じものを用いた。
（不織布Ａ）
　実施例１と同じものを用いた。
（不織布Ｂ）
　実施例１と同じものを用いた。
（不織布Ｃ）
　実施例２と同じものを用いた。
（濾材）
　濾材の構成については下記条件のものを用いた。
条件：不織布Ａと不織布Ｂの層間にアルデヒド吸着剤１００質量部および接着剤３０質量部を介在させ、不織布Ｂと不織布Ｃの層間にイオン交換樹脂１００質量部および接着剤３０質量部を介在させた濾材。 [Example 10]
(Aldehyde adsorbent)
The same as in Example 1 was used.
(glue)
The same as in Example 1 was used.
(Ion exchange resin)
The same as in Example 1 was used.
(Non-woven fabric A)
The same as in Example 1 was used.
(Non-woven fabric B)
The same as in Example 1 was used.
(Non-woven fabric C)
The same as in Example 2 was used.
(Filter material)
As for the composition of the filter medium, the one under the following conditions was used.
Condition: 100 parts by mass of an aldehyde adsorbent and 30 parts by mass of an adhesive were interposed between the nonwoven fabric A and the nonwoven fabric B, and 100 parts by mass of an ion exchange resin and 30 parts by mass of the adhesive were interposed between the nonwoven fabric B and the nonwoven fabric C. Filter media.
　［比較例１］
（無機多孔質体）
　実施例１と同じものを用いた。
（接着剤）
　実施例１と同じものを用いた。
（イオン交換樹脂）
　実施例３と同じものを用いた。
（活性炭）
　実施例３と同じものを用いた。
（不織布Ａ）
　実施例１と同じものを用いた。
（不織布Ｂ）
　実施例１と同じものを用いた。
（濾材）
　濾材の構成については下記条件のものを用いた。
条件：不織布Ａと不織布Ｂの層間に無機多孔質体１００質量部、接着剤９０質量部、イオン交換樹脂１００質量部および未添着活性炭１００質量部を介在させた濾材。 [Comparative Example 1]
(Inorganic porous body)
The same as in Example 1 was used.
(glue)
The same as in Example 1 was used.
(Ion exchange resin)
The same as in Example 3 was used.
(Activated carbon)
The same as in Example 3 was used.
(Non-woven fabric A)
The same as in Example 1 was used.
(Non-woven fabric B)
The same as in Example 1 was used.
(Filter material)
As for the composition of the filter medium, the one under the following conditions was used.
Condition: A filter medium in which 100 parts by mass of an inorganic porous body, 90 parts by mass of an adhesive, 100 parts by mass of an ion exchange resin and 100 parts by mass of unattached activated carbon are interposed between the layers of the non-woven fabric A and the non-woven fabric B.
　［比較例２］
（アルデヒド吸着剤）
　実施例１と同じものを用いた。
（接着剤）
　実施例１と同じものを用いた。
（活性炭）
　実施例３同じものを用いた。
（不織布Ａ）
　実施例１と同じものを用いた。
（不織布Ｂ）
　実施例１と同じものを用いた。
（濾材）
　濾材の構成については下記条件のものを用いた。
条件：不織布Ａと不織布Ｂの層間にアルデヒド吸着剤１００質量部、未添着活性炭１００質量部および接着剤６０質量部を介在させた濾材。 [Comparative Example 2]
(Aldehyde adsorbent)
The same as in Example 1 was used.
(glue)
The same as in Example 1 was used.
(Activated carbon)
Example 3 The same thing was used.
(Non-woven fabric A)
The same as in Example 1 was used.
(Non-woven fabric B)
The same as in Example 1 was used.
(Filter material)
As for the composition of the filter medium, the one under the following conditions was used.
Condition: A filter medium in which 100 parts by mass of an aldehyde adsorbent, 100 parts by mass of unattached activated carbon and 60 parts by mass of an adhesive are interposed between the nonwoven fabric A and the nonwoven fabric B.
　各実施例、比較例の濾材の構成と特性を表１にまとめた。 Table 1 summarizes the configurations and characteristics of the filter media of each example and comparative example.
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１～１０の濾材は、アミン系化合物として酸ヒドラジド類を添着した無機多孔質体を有しているため、アセトアルデヒドの脱臭性能に優れる結果が得られ、イオン交換樹脂を有しているため、アンモニアの脱臭性能に優れる結果が得られ、いずれも臭気を感じる度合いが低かった。 Since the filter media of Examples 1 to 10 have an inorganic porous body impregnated with acid hydrazides as an amine compound, excellent results in deodorizing performance of acetaldehyde can be obtained, and they have an ion exchange resin. The results of excellent deodorizing performance of ammonia were obtained, and the degree of odor was low in all cases.
　実施例１～７の濾材は活性炭を有しているため、活性炭を有していない実施例８～１０の濾材と比べて、酢酸の脱臭性能に優れる結果が得られた。特に実施例１、２および６の濾材は、炭酸水素ナトリウムを添着した活性炭を有しているため、炭酸水素ナトリウムを添着していない実施例３、４、５および７の濾材に比べて、さらに酢酸の脱臭性能に優れる結果が得られた。 Since the filter media of Examples 1 to 7 had activated carbon, the results obtained that the deodorizing performance of acetic acid was superior to that of the filter media of Examples 8 to 10 having no activated carbon. In particular, since the filter media of Examples 1, 2 and 6 have activated carbon impregnated with sodium hydrogen carbonate, they are further compared with the filter media of Examples 3, 4, 5 and 7 not impregnated with sodium hydrogen carbonate. The result was that the deodorizing performance of acetic acid was excellent.
　実施例１、２、３、４、５、９および１０の濾材は粒子径が小さいイオン交換樹脂を有しているため、粒子径が大きいイオン交換樹脂を有した実施例６～８の濾材と比べて、アンモニアの脱臭性能に優れる結果が得られた。 Since the filter media of Examples 1, 2, 3, 4, 5, 9 and 10 have an ion exchange resin having a small particle size, the filter media of Examples 6 to 8 have an ion exchange resin having a large particle size. In comparison, the results obtained that the deodorizing performance of ammonia was excellent.
　実施例２は実施例１と比較し、炭酸水素ナトリウム添着活性炭とアルデヒド吸着剤およびイオン交換樹脂を異層に配置しているため、活性炭およびアルデヒドに添着している薬剤が互いに影響を受けず特に脱臭性能および二次発臭抑制に効果がある結果が得られた。 Compared with Example 1, in Example 2, the activated carbon impregnated with sodium hydrogen carbonate, the aldehyde adsorbent, and the ion exchange resin are arranged in different layers, so that the activated carbon and the chemicals adhering to the aldehyde are not affected by each other. Results were obtained that were effective in deodorizing performance and suppressing secondary odor.
　実施例３の濾材は未添着活性炭として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０．４２ｃｃ／ｇ、ＭＰ法により算出される細孔径が０．４ｎｍ以上の細孔の細孔容積に対する、細孔径が０．４～２ｎｍの細孔の細孔容積の比率が８６％の活性炭を用いているため実施例４および実施例５と比較し、二次発臭を抑制した結果が得られた。 In the filter medium of Example 3, the pore volume of pores having a pore diameter of 0.4 to 2 nm calculated by the MP method as unattached activated carbon is 0.42 cc / g, and the pore diameter calculated by the MP method is 0.4 nm. Since activated carbon is used in which the ratio of the pore volume of the pores having a pore diameter of 0.4 to 2 nm to the pore volume of the above pores is 86%, it is compared with Examples 4 and 5 and is secondary. The result of suppressing the odor was obtained.
　実施例９の濾材はアルデヒド吸着剤とイオン交換樹脂を同層に有しているため、実施例１０のアルデヒド吸着剤とイオン交換樹脂を同層に有していない濾材と比較し、アンモニア、アセトアルデヒドガスを効率的に除去し、かつ吸着剤に一旦吸着されたこれらのガスを同層に介在するもう一方の吸着剤が除去することで二次発臭を抑制した結果が得られた。 Since the filter medium of Example 9 has an aldehyde adsorbent and an ion exchange resin in the same layer, ammonia and acetaldehyde are compared with the filter medium having no aldehyde adsorbent and an ion exchange resin in the same layer of Example 10. The results obtained that the secondary odor was suppressed by efficiently removing the gas and removing these gases once adsorbed by the adsorbent by the other adsorbent interposed in the same layer.
　比較例１の濾材は、アルデヒド吸着剤を有していないので、アルデヒドの脱臭性能が劣る結果が得られ、比較例２の濾材は、イオン交換樹脂を有していないので、アンモニアの脱臭性能が劣る結果が得られ、どちらも臭気を感じる度合いが高かった。 Since the filter medium of Comparative Example 1 does not have an aldehyde adsorbent, the deodorizing performance of aldehyde is inferior, and the filter medium of Comparative Example 2 does not have an ion exchange resin, so that the deodorizing performance of ammonia is poor. Inferior results were obtained, and both had a high degree of odor.
　本発明の濾材は、アンモニアやアルデヒド類といった極性ガスの吸着性能に優れ、かつ長期間使用時における二次発臭の問題が少ない。特に高齢者施設等の室内臭気として問題視されているペット臭の空気を清浄化するためのエアフィルターとして好ましく使用される。 The filter medium of the present invention has excellent adsorption performance for polar gases such as ammonia and aldehydes, and has few problems of secondary odor during long-term use. In particular, it is preferably used as an air filter for purifying pet odor air, which is regarded as a problem as indoor odor in facilities for the elderly.

Claims (6)

  1. 　積層された少なくとも２枚の不織布を有し、前記積層された不織布の層間の少なくとも１つの層間に、少なくとも酸ヒドラジド類が担持された無機多孔質体と酸性カチオン交換樹脂を含む、濾材。 A filter medium having at least two laminated non-woven fabrics and containing an inorganic porous body in which at least acid hydrazides are supported between at least one layer between the laminated non-woven fabrics and an acidic cation exchange resin.
  2. 　前記酸性カチオン交換樹脂が粒子状である、請求項１に記載の濾材。 The filter medium according to claim 1, wherein the acidic cation exchange resin is in the form of particles.
  3. 　前記酸性カチオン交換樹脂の平均粒子径が２００μｍ以下である、請求項２に記載の濾材。 The filter medium according to claim 2, wherein the average particle size of the acidic cation exchange resin is 200 μm or less.
  4. 　積層された不織布の層間の少なくとも１つに活性炭が含まれる、請求項１～３いずれかに記載の濾材。 The filter medium according to any one of claims 1 to 3, wherein activated carbon is contained in at least one of the layers of the laminated non-woven fabric.
  5. 　ＭＰ法により算出される活性炭の細孔径が０．４ｎｍ以上、２ｎｍ以下である細孔の細孔容積が０．４０ｃｃ／ｇ以上、０．５５ｃｃ／ｇ以下の範囲であり、かつ、ＭＰ法およびＢＪＨ法により算出される細孔径が０．４ｎｍ以上の細孔の細孔容積に対する、細孔径が０．４ｎｍ以上、２ｎｍ以下である細孔の細孔容積の比率が７５％以上である、請求項４に記載の濾材。 The pore volume of the activated carbon calculated by the MP method is 0.4 nm or more and 2 nm or less, and the pore volume is in the range of 0.40 cc / g or more and 0.55 cc / g or less, and the MP method and Claimed that the ratio of the pore volume of pores having a pore diameter of 0.4 nm or more and 2 nm or less to the pore volume of pores having a pore diameter of 0.4 nm or more calculated by the BJH method is 75% or more. Item 4. The filter medium according to Item 4.
  6. 　前記活性炭がアルカリ添着活性炭である、請求項４または５に記載の濾材。 The filter medium according to claim 4 or 5, wherein the activated carbon is an alkali-impregnated activated carbon.
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