JP4911706B2 - Deodorant filter - Google Patents
Deodorant filter Download PDFInfo
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- JP4911706B2 JP4911706B2 JP2007048698A JP2007048698A JP4911706B2 JP 4911706 B2 JP4911706 B2 JP 4911706B2 JP 2007048698 A JP2007048698 A JP 2007048698A JP 2007048698 A JP2007048698 A JP 2007048698A JP 4911706 B2 JP4911706 B2 JP 4911706B2
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- activated carbon
- mixed paper
- carbon mixed
- phthalocyanine complex
- deodorizing filter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002781 deodorant agent Substances 0.000 title claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 221
- 230000001877 deodorizing effect Effects 0.000 claims description 77
- 229910052751 metal Inorganic materials 0.000 claims description 61
- 239000002184 metal Substances 0.000 claims description 61
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000002253 acid Substances 0.000 claims description 27
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 20
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 34
- 239000007789 gas Substances 0.000 description 26
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 18
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 229920002125 Sokalan® Polymers 0.000 description 16
- 235000019645 odor Nutrition 0.000 description 16
- 239000004584 polyacrylic acid Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 14
- 229910021529 ammonia Inorganic materials 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229910000365 copper sulfate Inorganic materials 0.000 description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 11
- 238000004332 deodorization Methods 0.000 description 11
- 235000013162 Cocos nucifera Nutrition 0.000 description 10
- 244000060011 Cocos nucifera Species 0.000 description 10
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- IYPQZXRHDNGZEB-UHFFFAOYSA-N cobalt sodium Chemical compound [Na].[Co] IYPQZXRHDNGZEB-UHFFFAOYSA-N 0.000 description 7
- -1 phthalocyanine carboxylic acid Chemical class 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- UBJVUCKUDDKUJF-UHFFFAOYSA-N Diallyl sulfide Chemical compound C=CCSCC=C UBJVUCKUDDKUJF-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000029142 excretion Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 2
- CSPHGSFZFWKVDL-UHFFFAOYSA-M (3-chloro-2-hydroxypropyl)-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)CCl CSPHGSFZFWKVDL-UHFFFAOYSA-M 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
Description
本発明は、家庭用または業務用の冷蔵庫、生ゴミ処理機、あるいはトイレなどにおける室内のいやな臭を取り除くフィルター材等として使用し、特にアンモニア、トリメチルアミン、硫化水素、メチルメルカプタン、二硫化ジメチルなどの臭気を効率的に分解浄化するフィルターに関する技術である。 The present invention is used as a filter material or the like for removing unpleasant odors in a room or refrigerator for home use or commercial use, particularly ammonia, trimethylamine, hydrogen sulfide, methyl mercaptan, dimethyl disulfide, etc. It is a technology related to a filter that efficiently decomposes and purifies odors.
臭気を効率的に浄化する消臭フィルターは、様々なものが開発されており、その消臭方法は、大きく分類して三種類にまとめられる。活性炭やゼオライト等の吸着材を利用した吸着タイプと、オゾンや光触媒、金属フタロシアニン錯体等により悪臭物質を分解除去する触媒タイプ、あるいはこの吸着タイプと触媒タイプを併用した併用タイプに分けられる。このうち例えば、活性炭の優れた吸着作用を利用した技術がよく知られているが、これらは悪臭成分を素早く吸着し、周辺の臭気濃度を即効的に低下させる働きに優れた方法であるが、悪臭成分の吸着量に限りがあり、飽和状態や、温度の上昇によっては、悪臭を再放出するという問題もあり、有効期間に限りのある消臭方法といわれている。また、オゾンによって悪臭物質を分解する方法は、設備が大がかりになったり、オゾンそのものが人体に有害であることもあってあまり採用されていない。光触媒によって悪臭物質を分解する方法は、反応が遅く即効性を要求される消臭フィルターに使われることは少ない。そこで、最近では以下に示すように、悪臭物質を酸化還元反応によって分解除去する金属フタロシアニン錯体等の触媒タイプと活性炭等の吸着タイプを組み合わせ、活性炭に吸着された臭気を金属フタロシアニン錯体等の触媒反応によって分解する方法が多く採用されている。 A variety of deodorizing filters that efficiently purify odors have been developed, and the deodorizing methods are roughly classified into three types. It is divided into an adsorption type using an adsorbent such as activated carbon and zeolite, a catalyst type that decomposes and removes malodorous substances by ozone, a photocatalyst, a metal phthalocyanine complex, or the like, or a combined type that uses this adsorption type and the catalyst type in combination. Among these, for example, techniques using the excellent adsorption action of activated carbon are well known, but these are methods that adsorb malodorous components quickly and are effective in quickly reducing the concentration of odors around, There is a limit to the amount of malodorous components adsorbed, and there is a problem that the malodorous odor is re-released depending on the saturation state and temperature rise. In addition, the method of decomposing malodorous substances with ozone is not widely adopted because the equipment becomes large and ozone itself is harmful to the human body. The method of decomposing malodorous substances with a photocatalyst is rarely used in a deodorizing filter that is slow in reaction and requires immediate effect. Therefore, recently, as shown below, a combination of a catalytic type such as a metal phthalocyanine complex that decomposes and removes malodorous substances by oxidation-reduction reaction and an adsorption type such as activated carbon, and the odor adsorbed on the activated carbon is converted into a catalytic reaction such as a metal phthalocyanine complex. Many methods of disassembling are employed.
特許文献１においては、金属フタロシアニン錯体にダイマーの形成を防ぐ方法を開示し、金属フタロシアニン錯体の触媒活性の低下を防いだ消臭フィルターの製造方法が記載されている。 Patent Document 1 discloses a method for preventing the formation of a dimer in a metal phthalocyanine complex, and a method for producing a deodorizing filter that prevents a decrease in the catalytic activity of the metal phthalocyanine complex.
特許文献２においては、消臭能力および消臭速度に優れたゲル状消臭剤として、２０００％以上の水分を吸収しゲル化した吸水性樹脂中に、金属フタロシアニンカルボン酸あるいは金属フタロシアニンスルホン酸および／または遷移金属イオンの炭酸塩、硫酸塩、酢酸塩等の塩類、および金属酸化物を含有させたゲル状消臭剤が開示されており、通常のゲル化していない酸化還元能を有する金属錯体および／または遷移金属イオン担持樹脂と比較して消臭能力および消臭速度に優れ、特に水溶性の悪臭に対して極めて効果の有るものとして記載されている。 In Patent Document 2, as a gel-like deodorant excellent in deodorizing ability and deodorizing speed, a metal phthalocyanine carboxylic acid or metal phthalocyanine sulfonic acid and Disclosed is a gel-type deodorant containing transition metal ion carbonates, sulfates, acetates and the like, and metal oxides, and a metal complex having a normal non-gelled redox ability It is described as having excellent deodorizing ability and deodorizing speed as compared with a transition metal ion-supporting resin, and particularly effective for water-soluble malodor.
また、出願人は特許文献３を出願しており、高いｐＨ環境にした第１消臭フィルターと、低いｐＨ環境にした第２消臭フィルターとを備え、前記第１消臭フィルター及び／または第２消臭フィルターは、活性炭混抄紙に金属フタロシアニン錯体を担持させたものからなり、アンモニア、硫化水素、メチルメルカプタン、酢酸、アセトアルデヒド、ジメチルスルフィド等多くの種類の悪臭に対して優れた消臭性能を有するものとして開示している。 The applicant has applied for Patent Document 3 and includes a first deodorizing filter having a high pH environment and a second deodorizing filter having a low pH environment, and the first deodorizing filter and / or the second deodorizing filter. 2. The deodorizing filter consists of activated carbon mixed paper carrying a metal phthalocyanine complex, and has excellent deodorizing performance against many types of malodor such as ammonia, hydrogen sulfide, methyl mercaptan, acetic acid, acetaldehyde, dimethyl sulfide. It is disclosed as having.
これらの従来技術は、いずれも金属フタロシアニン錯体の優れた触媒能を用いて、効率的に脱臭する方法として有用な方法ではあるが、特にアンモニア、トリメチルアミン、硫化水素、メチルメルカプタン、二硫化ジメチルといった食品臭や排泄臭に多く含まれる悪臭に対して即効性があり、効果的であってしかも低コストである消臭フィルターが求められている。
本発明は、かかる技術的背景に鑑みてなされたものであって、低コストでありながら食品臭や排泄臭に多く含まれる悪臭を、素早く、効率よく分解浄化することのできる消臭フィルターを提供することを目的とする。
These conventional techniques are all useful methods for efficient deodorization using the excellent catalytic ability of metal phthalocyanine complexes. Particularly, foods such as ammonia, trimethylamine, hydrogen sulfide, methyl mercaptan, and dimethyl disulfide are used. There is a need for a deodorizing filter that is immediately effective against bad odors that are abundant in odors and excretion odors, and that is effective and low in cost.
The present invention has been made in view of such a technical background, and provides a deodorizing filter capable of quickly and efficiently decomposing and purifying malodors contained in food odors and excretion odors at a low cost. The purpose is to do.
前記目的を達成するために、本発明は以下の手段を提供する。 In order to achieve the above object, the present invention provides the following means.
［１］活性炭混抄紙に金属フタロシアニン錯体と、ポリカルボン酸と、金属塩を担持させたものからなることを特徴とする消臭フィルター。 [1] A deodorizing filter comprising an activated carbon mixed paper having a metal phthalocyanine complex, a polycarboxylic acid, and a metal salt supported thereon.
［２］前記消臭フィルターにおいて、金属フタロシアニン錯体がコバルトフタロシアニン錯体および鉄フタロシアニン錯体を担持させたものからなる前項１に記載の消臭フィルター。 [2] The deodorizing filter according to item 1 above, wherein the metal phthalocyanine complex comprises a cobalt phthalocyanine complex and an iron phthalocyanine complex supported thereon.
［３］前記金属フタロシアニン錯体の担持質量比が、コバルトフタロシアニン錯体／鉄フタロシアニン錯体＝９８／２〜５５／４５である前項２に記載の消臭フィルター。 [3] The deodorizing filter according to item 2 above, wherein the supported mass ratio of the metal phthalocyanine complex is cobalt phthalocyanine complex / iron phthalocyanine complex = 98/2 to 55/45.
［４］前記消臭フィルターにおいて、ポリカルボン酸が分子量１０００〜２００００のポリカルボン酸を担持させたものからなる前項１〜３のいずれか１項に記載の消臭フィルター。 [4] The deodorizing filter according to any one of items 1 to 3, wherein the deodorizing filter comprises a polycarboxylic acid carrying a polycarboxylic acid having a molecular weight of 1000 to 20000.
［５］前記消臭フィルターにおいて、金属塩が水溶性であり二価の銅又は亜鉛の化合物から選ばれる１もしくは複数の金属塩を担持させたものからなる前項１〜４のいずれか１項に記載の消臭フィルター。 [5] In the deodorizing filter, in any one of the preceding 1-4 consisting of those metal salts were carrying one or more metal salts selected from the compounds of divalent copper or zinc are water-soluble Deodorant filter as described.
［６］前記金属フタロシアニン錯体の担持量が活性炭混抄紙１ｇ当り２００〜２００００μｇの範囲である前項１〜５のいずれか１項に記載の消臭フィルター。 [6] The deodorizing filter according to any one of items 1 to 5, wherein the supported amount of the metal phthalocyanine complex is in the range of 200 to 20000 μg per 1 g of the activated carbon mixed paper.
［７］前記ポリカルボン酸の担持量が活性炭混抄紙１ｇ当り５００〜５００００μｇの範囲で、前記金属塩の担持量が活性炭混抄紙１ｇ当り５００〜５００００μｇの範囲である前項１〜６のいずれか１項に記載の消臭フィルター。
[7] Any one of items 1 to 6 above, wherein the supported amount of the polycarboxylic acid is in the range of 500 to 50000 μg per 1 g of the activated carbon mixed paper, and the supported amount of the metal salt is in the range of 500 to 50000 μg per 1 g of the activated carbon mixed paper. Deodorizing filter according to item.
［８］前記活性炭混抄紙において、活性炭含有率が活性炭混抄紙の４０〜８０質量％である前項１〜７のいずれか１項に記載の消臭フィルター。 [8] The deodorizing filter according to any one of items 1 to 7, wherein the activated carbon mixed paper has an activated carbon content of 40 to 80% by mass of the activated carbon mixed paper.
［１］の発明では、活性炭混抄紙に金属フタロシアニン錯体と、ポリカルボン酸と、金属塩を担持させたものからなる消臭フィルターであるので、活性炭の強力な吸着力により、アンモニア、トリメチルアミン、硫化水素、メチルメルカプタン、二硫化ジメチル等の悪臭は、素早く消臭フィルターに吸着され、金属フタロシアニン錯体の酸化力や、ポリカルボン酸の塩基性ガスに対する吸着力や、金属塩のアンモニアや硫化水素に対する吸着力によって効果的に分解浄化するものと考えられ、一種類のフィルターで酸・塩基性両方の悪臭ガスを効率的に消臭することができる。金属フタロシアニン錯体やポリカルボン酸、金属塩は、光触媒のように担持体を侵すことがない上に、バインダー樹脂を介さなくても活性炭混抄紙に直接担持されるので、消臭剤として非常に有効である。 In the invention of [1], since it is a deodorizing filter made of activated carbon mixed paper having a metal phthalocyanine complex, a polycarboxylic acid, and a metal salt supported thereon, ammonia, trimethylamine, sulfide, and the like due to the strong adsorption power of activated carbon. Malodors such as hydrogen, methyl mercaptan, and dimethyl disulfide are quickly adsorbed on the deodorizing filter, and the oxidizing power of metal phthalocyanine complexes, the adsorption power of polycarboxylic acids to basic gases, and the adsorption of metal salts to ammonia and hydrogen sulfide. It is thought that it effectively decomposes and purifies by force, and it is possible to efficiently deodorize both acid and basic malodorous gases with a single type of filter. Metal phthalocyanine complexes, polycarboxylic acids, and metal salts do not attack the support unlike photocatalysts, and are directly supported on activated carbon mixed paper without using a binder resin. It is.
［２］の発明では、金属フタロシアニン錯体がコバルトフタロシアニン錯体および鉄フタロシアニン錯体を担持させたものからなるので、両錯体の相乗作用によって特にジメチルスルフィド、ジアリルスルフィド、ジメチルジスルフィドの消臭除去率を顕著に向上させることができる。 In the invention of [2], since the metal phthalocyanine complex comprises a cobalt phthalocyanine complex and an iron phthalocyanine complex, the deodorization removal rate of dimethyl sulfide, diallyl sulfide, and dimethyl disulfide is particularly remarkable due to the synergistic action of both complexes. Can be improved.
［３］の発明では、前記金属フタロシアニン錯体の担持質量比が、コバルトフタロシアニン錯体／鉄フタロシアニン錯体＝９８／２〜５５／４５に設定されているから、両錯体の相乗作用が十分に発揮されてジメチルフルフィド、ジアリルスルフィド、ジメチルジスルフィドの消臭性能を一層向上させることができる。 In the invention of [3], since the supported mass ratio of the metal phthalocyanine complex is set to cobalt phthalocyanine complex / iron phthalocyanine complex = 98/2 to 55/45, the synergistic effect of both complexes is sufficiently exhibited. The deodorizing performance of dimethyl fluoride, diallyl sulfide and dimethyl disulfide can be further improved.
［４］の発明では、前記消臭フィルターにおいて、ポリカルボン酸が分子量１０００〜２００００のポリカルボン酸を担持させたものからなるので、活性炭の吸着性能を損ねることなくアンモニアやアミン等の塩基性ガスを吸着することができる。 In the invention of [4], in the deodorizing filter, since the polycarboxylic acid comprises a polycarboxylic acid having a molecular weight of 1000 to 20000, a basic gas such as ammonia or amine without impairing the adsorption performance of the activated carbon. Can be adsorbed.
［５］の発明では、前記消臭フィルターにおいて、金属塩が水溶性であり二価の銅又は亜鉛の化合物から選ばれる１もしくは複数の金属塩であるので、ポリカルボン酸水溶液と混合させることにより、カルボキシル基に配位し、フィルター材表面から脱落することなく存在する。また、二価の銅や二価の亜鉛の持つアンモニア、硫化水素、メチルメルカプタンに対する化学吸着力によってこれらの悪臭を同時に除去することができる。 In the invention [5], in the deodorizing filter, since it is one or more metal salts metal salt is selected from the compounds of divalent copper or zinc are water soluble, by mixing a polycarboxylic acid aqueous solution Coordinates to carboxyl groups and exists without falling off the filter material surface. Further, it is possible to simultaneously remove these malodors by chemical adsorption force ammonia, hydrogen sulfide, to methyl mercaptan with a divalent copper and divalent zinc.
［６］の発明では、前記金属フタロシアニン錯体の担持量が活性炭混抄紙１ｇ当り２００〜２００００μｇの範囲に設定されているから十分な消臭性能を得ることができる。 In the invention of [6], since the supported amount of the metal phthalocyanine complex is set in the range of 200 to 20000 μg per 1 g of the activated carbon mixed paper, a sufficient deodorizing performance can be obtained.
［７］の発明では、前記ポリカルボン酸の担持量が活性炭混抄紙１ｇ当り５００〜５００００μｇの範囲であるので、活性炭の細孔を被覆することなく、多量の塩基性ガスを吸着することができる。また、前記金属塩の担持量が活性炭混抄紙１ｇ当り５００〜５００００μｇの範囲であるので、十分な量の塩基性ガスと酸性ガスを吸着することができる。 In the invention of [7], since the amount of the polycarboxylic acid supported is in the range of 500 to 50000 μg per gram of the activated carbon mixed paper, a large amount of basic gas can be adsorbed without covering the pores of the activated carbon. . Further, since the supported amount of the metal salt is in the range of 500 to 50000 μg per 1 g of the activated carbon mixed paper, a sufficient amount of basic gas and acid gas can be adsorbed.
［８］の発明では、前記活性炭混抄紙において、活性炭含有率が活性炭混抄紙の４０〜８０質量％であるので、十分な吸着効果の得られるものとなり、また活性炭の脱落もなく、紙としての強度も確保することができる。 In the invention of [8], since the activated carbon content in the activated carbon mixed paper is 40 to 80% by mass of the activated carbon mixed paper, a sufficient adsorption effect can be obtained, and the activated carbon does not fall off and is used as paper. Strength can also be secured.
この発明の消臭フィルターは、活性炭混抄紙に金属フタロシアニン錯体と、ポリカルボン酸と、金属塩を担持させた後、ハニカム形状に加工し消臭フィルターとしてもよいし、活性炭混抄紙をハニカム形状に加工してフィルター化してから、金属フタロシアニン錯体と、ポリカルボン酸と、金属塩を担持させて消臭フィルターとしてもかまわない。また、消臭フィルターの大きさや厚みについては、必要とされる消臭能力に応じて決めればよい。使い方としては、例えば、ファン等の前後に設置して、悪臭ガスを該消臭フィルター内に通過せしめることによって消臭を行なうことができる。 The deodorizing filter of the present invention may be a deodorizing filter obtained by supporting a metal phthalocyanine complex, a polycarboxylic acid, and a metal salt on an activated carbon mixed paper and then processing the honeycomb into a honeycomb shape. After processing and forming a filter, a metal phthalocyanine complex, a polycarboxylic acid, and a metal salt may be supported to form a deodorizing filter. The size and thickness of the deodorizing filter may be determined according to the required deodorizing ability. As usage, for example, it can be deodorized by installing it before and after a fan or the like and allowing malodorous gas to pass through the deodorizing filter.
前記活性炭混抄紙は通常の湿式抄紙法により製造できる。例えば活性炭と天然パルプを水に添加し、水スラリーを作成する。そのスラリーを攪拌しながら所定の固形分濃度に調整し、その後カチオン系ポリマー又はアニオン系ポリマーを添加し、得られた凝集体水分散液を、抄紙機を使い湿式抄紙法によりシート化し、乾燥処理を行なうことによって活性炭混抄紙を得る。次に、この活性炭混抄紙を、コルゲート加工機を用いて、例えばハニカム形状に加工しフィルターの形状にする。前記活性炭混抄紙によるハニカムフィルターは活性炭の強い吸着力によって悪臭ガスの吸着体の役割をなすものである。 The activated carbon mixed paper can be produced by a normal wet paper making method. For example, activated carbon and natural pulp are added to water to create a water slurry. The slurry is adjusted to a predetermined solid content concentration while stirring, and then a cationic polymer or an anionic polymer is added, and the resulting aggregate aqueous dispersion is formed into a sheet by a wet papermaking method using a paper machine and dried. To obtain an activated carbon mixed paper. Next, this activated carbon mixed paper is processed into, for example, a honeycomb shape by using a corrugating machine to obtain a filter shape. The honeycomb filter made of the activated carbon mixed paper serves as an adsorbent for malodorous gas due to the strong adsorptive power of the activated carbon.
この発明に使用する活性炭としては、椰子殻活性炭、石油ピッチ系球状活性炭、活性炭素繊維、木質系活性炭等の活性炭系炭素多孔質体が、吸着比表面積が非常に高いことから好ましく用いられる。中でも、椰子殻活性炭を用いるのが特に好ましい。 As the activated carbon used in the present invention, activated carbon-based carbon porous bodies such as coconut shell activated carbon, petroleum pitch-based spherical activated carbon, activated carbon fiber, and wood-based activated carbon are preferably used because of their very high adsorption specific surface area. Among them, it is particularly preferable to use coconut shell activated carbon.
また、前記活性炭混抄紙に使用する繊維としては、天然パルプ、ポリオレフィン及びアクリル繊維などのフィブリル化繊維を用いればよいが、金属フタロシアニン錯体の担持のし易さから天然パルプが特に好ましい。 Further, as the fiber used for the activated carbon mixed paper, fibrillated fibers such as natural pulp, polyolefin and acrylic fiber may be used, but natural pulp is particularly preferable because of easy loading of the metal phthalocyanine complex.
この発明の消臭フィルターに用いる金属フタロシアニン錯体は、特に限定されるものではないが、例えば鉄フタロシアニン錯体、コバルトフタロシアニン錯体が挙げられる。これらの中でもコバルトフタロシアニン錯体を用いるのが好ましく、この場合には、特にメチルメルカプタン、酢酸に対する消臭性能をさらに向上させることができる利点がある。前記コバルトフタロシアニン錯体としては、特に限定されるものではないが、例えばコバルトフタロシアニンポリスルホン酸ナトリウム、コバルトフタロシアニンオクタカルボン酸、コバルトフタロシアニンテトラカルボン酸等が挙げられる。前記鉄フタロシアニン錯体としては、特に限定されるものではないが、例えば鉄フタロシアニンテトラカルボン酸、鉄フタロシアニンオクタカルボン酸等が挙げられる。 Although the metal phthalocyanine complex used for the deodorizing filter of this invention is not specifically limited, For example, an iron phthalocyanine complex and a cobalt phthalocyanine complex are mentioned. Among these, it is preferable to use a cobalt phthalocyanine complex, and in this case, there is an advantage that the deodorizing performance with respect to methyl mercaptan and acetic acid can be further improved. The cobalt phthalocyanine complex is not particularly limited, and examples thereof include sodium cobalt phthalocyanine polysulfonate, cobalt phthalocyanine octacarboxylic acid, cobalt phthalocyanine tetracarboxylic acid and the like. The iron phthalocyanine complex is not particularly limited, and examples thereof include iron phthalocyanine tetracarboxylic acid and iron phthalocyanine octacarboxylic acid.
さらに好ましい構成は、前記金属フタロシアニン錯体としてコバルトフタロシアニン錯体及び鉄フタロシアニン錯体を併用した構成である。前記両錯体の担持質量比は、コバルトフタロシアニン錯体／鉄フタロシアニン錯体＝９８／２〜５５／４５に設定されるのが好ましい。このような比率範囲であれば、両錯体の相乗作用が十分に発揮されてジメチルスルフィド、ジアリルスルフィド、ジメチルジスルフィドの消臭性能を一層向上させることができる。上記範囲を逸脱した場合には両錯体の相乗作用が殆ど得られない。中でも両錯体の担持質量比は、コバルトフタロシアニン錯体／鉄フタロシアニン錯体＝９５／５〜８５／１５に設定されるのが特に好ましい。 A more preferable configuration is a configuration in which a cobalt phthalocyanine complex and an iron phthalocyanine complex are used in combination as the metal phthalocyanine complex. The supported mass ratio of both the complexes is preferably set to cobalt phthalocyanine complex / iron phthalocyanine complex = 98/2 to 55/45. Within such a ratio range, the synergistic action of both complexes is sufficiently exhibited, and the deodorizing performance of dimethyl sulfide, diallyl sulfide, and dimethyl disulfide can be further improved. When deviating from the above range, the synergistic action of both complexes is hardly obtained. Among them, the supported mass ratio of both complexes is particularly preferably set to cobalt phthalocyanine complex / iron phthalocyanine complex = 95/5 to 85/15.
金属フタロシアニン錯体を活性炭混抄紙に担持する前に、活性炭混抄紙をカチオン化処理することが望ましい。これは、金属フタロシアニン錯体の担持量を増大するための処理で、カチオン化処理は活性炭混抄紙の化学構造中にカチオン基を導入付与し得るものであればどのような処理であっても良い。中でも４級アンモニウム塩によりカチオン化処理が行われるのが好ましく、この場合には、金属フタロシアニン錯体の担持量をより増大させることができる利点がある。前記４級アンモニウム塩としては、例えば３―クロロ―２−ヒドロキシルプロピルトリメチルアンモニウムクロライド、グリシジルトリメチルアンモニウムクロライド、３―クロロ―２−ヒドロキシプロピルトリメチルアンモニウムクロライドの縮合ポリマー等が挙げられる。 Prior to supporting the metal phthalocyanine complex on the activated carbon mixed paper, it is desirable to cationize the activated carbon mixed paper. This is a treatment for increasing the supported amount of the metal phthalocyanine complex, and the cationization treatment may be any treatment as long as it can introduce and impart a cation group into the chemical structure of the activated carbon mixed paper. Of these, cationization is preferably performed with a quaternary ammonium salt. In this case, there is an advantage that the amount of the metal phthalocyanine complex supported can be further increased. Examples of the quaternary ammonium salt include 3-chloro-2-hydroxylpropyltrimethylammonium chloride, glycidyltrimethylammonium chloride, and 3-chloro-2-hydroxypropyltrimethylammonium chloride condensation polymer.
前記カチオン化処理された活性炭混抄紙によるフィルター（ハニカムフィルター等）を水洗し乾燥したあと、金属フタロシアニン錯体の水溶液に含浸させ、しかる後に水洗し乾燥し、金属フタロシアニン錯体を担持したフィルターを得る。 A filter (honeycomb filter or the like) made of activated carbon mixed paper subjected to cationization treatment is washed with water and dried, then impregnated with an aqueous solution of a metal phthalocyanine complex, and then washed with water and dried to obtain a filter carrying the metal phthalocyanine complex.
前記金属フタロシアニン錯体の担持量は活性炭混抄紙１ｇ当り２００〜２００００μｇの範囲であるのが好ましい。２００μｇ未満では、分解速度が著しく低下するので好ましくない。一方、金属フタロシアニン錯体が２００００μｇを超えると、消臭効果のこれ以上の増大は殆ど望めないばかりか、徒にコストを増大させるので好ましくない。中でも、金属フタロシアニン錯体の担持量は、活性炭混抄紙１ｇ当り３００〜３０００μｇの範囲とするのが特に好ましい。 The supported amount of the metal phthalocyanine complex is preferably in the range of 200 to 20000 μg per 1 g of the activated carbon mixed paper. If it is less than 200 μg, the decomposition rate is remarkably lowered, which is not preferable. On the other hand, if the amount of the metal phthalocyanine complex exceeds 20000 μg, not only a further increase in the deodorizing effect can be expected, but also the cost is increased undesirably. Among them, the amount of the metal phthalocyanine complex supported is particularly preferably in the range of 300 to 3000 μg per 1 g of the activated carbon mixed paper.
次に、この発明の消臭フィルターに用いるポリカルボン酸は、特に限定されるものではないが、例えばポリマレイン酸、アクリル酸−マレイン酸共重合体、ポリアクリル酸等が挙げられアンモニアやアミン等の塩基性ガスを多量に吸着する働きがある。また前記ポリカルボン酸の分子量は１０００〜２００００のポリカルボン酸であるのが好ましい。この範囲を逸脱するとポリカルボン酸が活性炭の細孔を被覆し吸着能力を低下させることとなり好ましくない。さらに、前記ポリカルボン酸の担持量は、活性炭混抄紙１ｇ当り５００〜５００００μｇの範囲であるのが好ましい。５００μｇを下回ると十分な量の塩基性ガスを吸着できない。５００００μｇを上回っても金属フタロシアニン錯体の表面を覆うことになり、その酸化による分解能力を低下させることとなり好ましくない。より好ましくは、活性炭混抄紙１ｇ当り２０００〜１００００μｇの範囲である。 Next, the polycarboxylic acid used in the deodorizing filter of the present invention is not particularly limited, and examples thereof include polymaleic acid, acrylic acid-maleic acid copolymer, polyacrylic acid, and the like such as ammonia and amine. It works to adsorb a large amount of basic gas. The polycarboxylic acid preferably has a molecular weight of 1000 to 20000. If it deviates from this range, the polycarboxylic acid is not preferable because it covers the pores of the activated carbon and lowers the adsorption capacity. Further, the amount of the polycarboxylic acid supported is preferably in the range of 500 to 50000 μg per 1 g of the activated carbon mixed paper. If it is less than 500 μg, a sufficient amount of basic gas cannot be adsorbed. Even if it exceeds 50,000 μg, the surface of the metal phthalocyanine complex is covered, and the decomposition ability due to oxidation thereof is lowered, which is not preferable. More preferably, it is the range of 2000-10000 microgram per 1g of activated carbon mixed paper.
また、この発明の消臭フィルターに用いる金属塩は、二価の銅又は亜鉛の水溶性の塩から選ばれる１もしくは複数の金属塩が好ましい。金属塩は、ポリカルボン酸の水溶液と混合させることによりカルボキシル基に配位しフィルターの表面から脱落することなく安定して存在し、中心金属である二価の銅又は亜鉛の持つ塩基性及び酸性ガスに対する吸着能力により、これらの悪臭ガスを同時に除去することができるものである。前記金属塩の担持量は、活性炭混抄紙１ｇ当り５００〜５００００μｇの範囲であるのが好ましい。５００μｇを下回ると十分な量の悪臭を除去することができなくなり、５００００μｇを上回っても水洗工程で脱落してしまうので好ましくない。より好ましくは、活性炭混抄紙１ｇ当り２０００〜１００００μｇの範囲である。 The metal salt used in the deodorizing filter of the present invention, one or more metal salts are preferable selected from divalent copper or zinc water soluble salt. Metal salt is present stably without falling off from the coordinated surface of the filter to a carboxyl group by mixing with an aqueous solution of a polycarboxylic acid, basic and acidic with a divalent copper or zinc, which is the center metal These malodorous gases can be removed at the same time due to the ability to adsorb gas. The amount of the metal salt supported is preferably in the range of 500 to 50000 μg per 1 g of the activated carbon mixed paper. If it is less than 500 μg, a sufficient amount of bad odor cannot be removed, and even if it exceeds 50,000 μg, it will drop off in the washing step, which is not preferable. More preferably, it is the range of 2000-10000 microgram per 1g of activated carbon mixed paper.
本発明の消臭フィルターの形状は特に限定されない。例えば平面的なシート状に形成されても良いし、波型形状のシートに成形されてもよいし、或いは、ハニカム構造に形成されてもよく、消臭フィルターを消臭対象ガスが通過するように構成されていればよい。また、消臭するガスの種類、濃度によって消臭フィルターの厚みや大きさ等を適宜変更することもできる。 The shape of the deodorizing filter of the present invention is not particularly limited. For example, it may be formed into a flat sheet, may be formed into a corrugated sheet, or may be formed into a honeycomb structure so that the deodorizing target gas passes through the deodorizing filter. It suffices to be configured. In addition, the thickness and size of the deodorizing filter can be appropriately changed depending on the type and concentration of the gas to be deodorized.
また、前記活性炭混抄紙における活性炭含有率は４０〜８０質量％であるのが好ましい。４０質量％未満では、悪臭ガスの吸着スピードが低下するので好ましくない。また、活性炭が８０質量％を越えて担持させると、必然的に活性炭混抄紙における繊維の割合が減少する結果、フィルターとしての物理的な強度が低下するので好ましくない。中でも、活性炭混抄紙は、活性炭含有率が５５〜７５質量％であるのがより好ましい。 Moreover, it is preferable that the activated carbon content rate in the said activated carbon mixed paper is 40-80 mass%. If it is less than 40% by mass, the adsorption speed of malodorous gas decreases, which is not preferable. On the other hand, when the activated carbon is supported in excess of 80% by mass, the ratio of fibers in the activated carbon mixed paper is inevitably reduced, resulting in a decrease in physical strength as a filter. Among them, the activated carbon mixed paper preferably has an activated carbon content of 55 to 75% by mass.
また、本発明の消臭フィルターにおいては、前記活性炭混抄紙に発明を妨げない範囲で、さらに他の消臭剤や臭気吸着剤や添加剤等を担持せしめた構成を採用しても良い。 Moreover, in the deodorizing filter of this invention, you may employ | adopt the structure which carry | supported other deodorizing agents, an odor adsorbent, an additive, etc. in the range which does not prevent invention in the said activated carbon mixed paper.
次ぎに実施例により、本発明を具体的に説明する。なお実施例における各種消臭性能の測定は次のように行った。
（アンモニア消臭性能）
消臭フィルターから切り出した円形試験片（直径５０ｍｍ厚さ２０ｍｍ重量１０ｇ）を長尺の円筒管の中間位置に配置されたサンプルホルダーに固定し、円筒の一端から毎分５リットルの通気を行なうファンをセットした試験キットを内容量２５０リットルのアクリルボックス内に入れた後、ボックス内において濃度が１００ｐｐｍとなるようにアンモニアガスを注入し、１時間経過後にアンモニアガスの残存濃度を測定し、この測定値よりアンモニアガスを除去した総量を算出し、これよりアンモニアガスの除去率（％）を算出した。
Next, the present invention will be described specifically by way of examples. In addition, the measurement of various deodorizing performance in an Example was performed as follows.
(Ammonia deodorization performance)
A circular test piece cut out from a deodorizing filter (diameter 50 mm, thickness 20 mm, weight 10 g) is fixed to a sample holder placed at an intermediate position of a long cylindrical tube, and a fan that ventilates 5 liters per minute from one end of the cylinder After placing the test kit in which it was set in an acrylic box with an internal volume of 250 liters, ammonia gas was injected so that the concentration would be 100 ppm in the box, and the residual concentration of ammonia gas was measured after 1 hour. The total amount from which ammonia gas was removed was calculated from the value, and the ammonia gas removal rate (%) was calculated therefrom.
（硫化水素消臭性能）
アンモニアガスに代えて硫化水素ガスを用いてアクリルボックス内において濃度が１０ｐｐｍとなるように注入した以外は、上記アンモニア消臭性能測定と同様にして硫化水素の除去率（％）を算出した。
(Hydrogen sulfide deodorization performance)
The removal rate (%) of hydrogen sulfide was calculated in the same manner as in the ammonia deodorization performance measurement, except that hydrogen sulfide gas was used instead of ammonia gas and the concentration was 10 ppm in the acrylic box.
（メチルメルカプタン消臭性能）
アンモニアガスに代えてメチルメルカプタンガスを用いてアクリルボックス内において濃度が１０ｐｐｍとなるように注入した以外は、上記アンモニア消臭性能測定と同様にしてメチルメルカプタンガスの除去率（％）を算出した。
(Methyl mercaptan deodorization performance)
The methyl mercaptan gas removal rate (%) was calculated in the same manner as in the ammonia deodorization performance measurement except that methyl mercaptan gas was used instead of ammonia gas and the concentration was 10 ppm in the acrylic box.
（トリメチルアミン消臭性能）
アンモニアガスに代えてトリメチルアミンガスを用いてアクリルボックス内において濃度が１０ｐｐｍとなるように注入した以外は、上記アンモニア消臭性能測定と同様にして酢酸ガスの除去率（％）を算出した。
(Trimethylamine deodorization performance)
The acetic acid gas removal rate (%) was calculated in the same manner as in the ammonia deodorization performance measurement except that trimethylamine gas was used instead of ammonia gas and the concentration was 10 ppm in the acrylic box.
（二硫化ジメチル消臭性能）
アンモニアガスに代えて二硫化ジメチルガスを用いてアクリルボックス内において濃度が１０ｐｐｍとなるように注入した以外は、上記アンモニア消臭性能測定と同様にしてアセトアルデヒドの除去率（％）を算出した。
(Dimethyl disulfide deodorization performance)
The removal rate (%) of acetaldehyde was calculated in the same manner as the ammonia deodorization performance measurement, except that dimethyl disulfide gas was used instead of ammonia gas and the acryl box was injected so that the concentration became 10 ppm.
そして、除去率が９５％以上であるものを「◎」、除去率が９０％以上９５％未満であるものを「○」、除去率が８５％以上９０％未満であるものを「△」、除去率が８５％未満であるものを「×」とし「△」以上を合格と評価した。 The removal rate is 95% or more, “」 ”, the removal rate is 90% or more and less than 95%,“ ◯ ”, the removal rate is 85% or more and less than 90%,“ △ ”, The removal rate of less than 85% was evaluated as “x”, and “Δ” or higher was evaluated as acceptable.
＜実施例１＞
椰子殻活性炭７０質量部と天然パルプ３０質量部を水２００質量部に添加し、水スラリーを作成する。得られた凝集体水分散液を抄紙機を使い湿式抄紙法によりシート化し、乾燥処理を行ない活性炭混抄紙を得た。得られた活性炭混抄紙の一部をコルゲート加工機を用いて波型形状紙に加工した。この波型形状紙と平面形状紙を、エチレンー酢酸ビニル共重合体からなる接着剤で接着して積層し、セル密度が２３０セル／ｉｎｃｈ２、厚さ１０ｍｍのフィルター材を得た。このフィルター材を３―クロロ―２−ヒドロキシプロピルトリメチルアンモニウムクロライド水溶液にてカチオン化処理をした後、乾燥させた。次に、このカチオン化処理後のフィルター材を、０．５質量％のコバルトフタロシアニンポリスルホン酸ナトリウム水溶液に含浸した後、水洗して乾燥することによって、金属フタロシアニン錯体を担持したフィルター材を得た。コバルトフタロシアニンポリスルホン酸ナトリウムの活性炭混抄紙への担持量は、活性炭混抄紙１ｇ当り４００μｇであった。次にこのフィルター材を、１．０質量％のポリアクリル酸（平均分子量５０００）と１．０質量％の硫酸銅の水溶液に含浸した後、水洗して乾燥して消臭フィルターを得た。ポリアクリル酸と硫酸銅の活性炭混抄紙への担持量は、活性炭混抄紙１ｇ当り５０００μｇと４０００μｇであった。また、活性炭混抄紙における椰子殻活性炭の含有率は７０質量％であった。上記の各種ガスの消臭試験をおこない除去率を表に記載した。
<Example 1>
70 parts by mass of coconut shell activated carbon and 30 parts by mass of natural pulp are added to 200 parts by mass of water to prepare a water slurry. The obtained aqueous dispersion of aggregate was formed into a sheet by a wet papermaking method using a paper machine and dried to obtain an activated carbon mixed paper. Part of the obtained activated carbon mixed paper was processed into corrugated paper using a corrugating machine. The corrugated paper and the flat paper were laminated by bonding with an adhesive made of an ethylene-vinyl acetate copolymer to obtain a filter material having a cell density of 230 cells / inch 2 and a thickness of 10 mm. This filter material was cationized with an aqueous 3-chloro-2-hydroxypropyltrimethylammonium chloride solution and then dried. Next, the filter material after the cationization treatment was impregnated with a 0.5% by mass aqueous solution of cobalt phthalocyanine polysulfonate, and then washed with water and dried to obtain a filter material carrying a metal phthalocyanine complex. The amount of sodium cobalt phthalocyanine polysulfonate supported on the activated carbon mixed paper was 400 μg per 1 g of the activated carbon mixed paper. Next, the filter material was impregnated with an aqueous solution of 1.0% by mass of polyacrylic acid (average molecular weight 5000) and 1.0% by mass of copper sulfate, washed with water and dried to obtain a deodorizing filter. The amounts of polyacrylic acid and copper sulfate supported on the activated carbon mixed paper were 5000 μg and 4000 μg per 1 g of the activated carbon mixed paper. Moreover, the content rate of the coconut shell activated carbon in activated carbon mixed paper was 70 mass%. The above-mentioned various gases were deodorized and the removal rates were listed in the table.
＜実施例２＞
次に、実施例１において、０．５質量％のコバルトフタロシアニンポリスルホン酸ナトリウム水溶液にかえて、０．６質量％のコバルトフタロシアニンポリスルホン酸ナトリウムと０．４質量％の鉄フタロシアニンテトラカルボン酸水溶液とした以外は実施例１と同様にして、消臭フィルターを得た。コバルトフタロシアニンポリスルホン酸ナトリウムと鉄フタロシアニンテトラカルボン酸の活性炭混抄紙への担持量は、活性炭混抄紙１ｇ当りそれぞれ４５０μｇ、３００μｇであった。
<Example 2>
Next, in Example 1, 0.6 mass% sodium cobalt phthalocyanine polysulfonate and 0.4 mass% iron phthalocyanine tetracarboxylic acid aqueous solution were used instead of 0.5 mass% cobalt phthalocyanine polysulfonate aqueous solution. Except for this, a deodorizing filter was obtained in the same manner as in Example 1. The supported amounts of cobalt phthalocyanine polysulfonate sodium and iron phthalocyanine tetracarboxylic acid on the activated carbon mixed paper were 450 μg and 300 μg, respectively, per 1 g of the activated carbon mixed paper.
＜実施例３＞
実施例１において、金属フタロシアニン錯体水溶液として、０．４８５質量％のコバルトフタロシアニンポリスルホン酸ナトリウムと、０．０１５質量％の鉄フタロシアニンテトラカルボン酸ナトリウムを用いた以外は実施例１と同様にして、消臭フィルター１を得た。なお、金属フタロシアニン錯体（コバルト系及び鉄系の合計）の活性炭混抄紙への担持量は活性炭混抄紙１ｇ当り４００μｇであった。即ち、コバルトフタロシアニンポリスルホン酸ナトリウムの活性炭混抄紙への担持量は、活性炭混抄紙１ｇ当り３８８μｇであり、鉄フタロシアニンテトラカルボン酸ナトリウムの活性炭混抄紙への担持量は、活性炭混抄紙１ｇ当り１２μｇであった。
<Example 3>
In Example 1, the metal phthalocyanine complex aqueous solution was used in the same manner as in Example 1 except that 0.485% by mass of sodium cobalt phthalocyanine polysulfonate and 0.015% by mass of sodium iron phthalocyanine tetracarboxylate were used. An odor filter 1 was obtained. The amount of the metal phthalocyanine complex (cobalt-based and iron-based) supported on the activated carbon mixed paper was 400 μg per 1 g of the activated carbon mixed paper. That is, the supported amount of sodium cobalt phthalocyanine polysulfonate on activated carbon mixed paper was 388 μg per gram of activated carbon mixed paper, and the supported amount of iron phthalocyanine tetracarboxylate sodium on activated carbon mixed paper was 12 μg per gram of activated carbon mixed paper. It was.
＜実施例４＞
次に、実施例１において、１．５質量％のコバルトフタロシアニンポリスルホン酸ナトリウム水溶液に含浸した以外は実施例１と同様にして、消臭フィルターを得た。なお、得られた消臭フィルターにおいて、コバルトフタロシアニンポリスルホン酸ナトリウムの活性炭混抄紙への担持量は、活性炭混抄紙１ｇ当り１０００μｇであった。
<Example 4>
Next, in Example 1, a deodorizing filter was obtained in the same manner as in Example 1 except that it was impregnated with a 1.5 mass% aqueous solution of cobalt phthalocyanine polysulfonate. In the obtained deodorizing filter, the amount of cobalt phthalocyanine polysulfonate sodium supported on the activated carbon mixed paper was 1000 μg per 1 g of the activated carbon mixed paper.
＜実施例５＞
次に、実施例１において、椰子殻活性炭３０質量部と天然パルプ３０質量部を水２００質量部に添加し、水スラリーを作成するものとした以外は実施例１と同様にして、消臭フィルターを得た。なお、活性炭混抄紙における椰子殻活性炭の含有量は５０質量％であった。
<Example 5>
Next, in Example 1, a deodorizing filter was obtained in the same manner as in Example 1 except that 30 parts by mass of coconut shell activated carbon and 30 parts by mass of natural pulp were added to 200 parts by mass of water to prepare a water slurry. Got. The content of coconut shell activated carbon in the activated carbon mixed paper was 50% by mass.
＜実施例６＞
次に、実施例１において、１．０質量％の硫酸銅を１．０質量％の塩化亜鉛とした以外は、実施例１と同様にして消臭フィルターを得た。塩化亜鉛の活性炭混抄紙への担持量は、活性炭混抄紙１ｇ当り３５００μｇであった。
<Example 6>
Next, a deodorizing filter was obtained in the same manner as in Example 1 except that 1.0% by mass of copper sulfate was changed to 1.0% by mass of zinc chloride. The amount of zinc chloride supported on the activated carbon mixed paper was 3500 μg per 1 g of the activated carbon mixed paper.
＜実施例７＞
次に、実施例１と同様にして、１．０質量％のポリアクリル酸（平均分子量５０００）と１．０質量％の硫酸銅の水溶液に含浸した後、水洗して乾燥した後、さらに０．１質量％の硫酸銅の水溶液に含浸し水洗を行わずに乾燥して消臭フィルターを得た。硫酸銅の活性炭混抄紙への担持量は、活性炭混抄紙１ｇ当り１００００μｇであった。
<Example 7>
Next, after impregnating an aqueous solution of 1.0% by mass of polyacrylic acid (average molecular weight 5000) and 1.0% by mass of copper sulfate in the same manner as in Example 1, it was washed with water and dried, and further 0 A deodorizing filter was obtained by impregnating with an aqueous solution of 1% by mass of copper sulfate and drying without washing with water. The amount of copper sulfate supported on the activated carbon mixed paper was 10000 μg per 1 g of the activated carbon mixed paper.
＜実施例８＞
次に、実施例１において、１．０質量％のポリアクリル酸（平均分子量５０００）を０．２質量％のポリアクリル酸（平均分子量５０００）に含浸し水洗を行わずに乾燥した以外は、実施例１と同様にして消臭フィルターを得た。なお、ポリアクリル酸と硫酸銅の活性炭混抄紙への担持量は、活性炭混抄紙１ｇ当り４００００μｇと３２０００μｇであった。
<Example 8>
Next, in Example 1, except that 1.0% by mass of polyacrylic acid (average molecular weight 5000) was impregnated in 0.2% by mass of polyacrylic acid (average molecular weight 5000) and dried without washing. A deodorizing filter was obtained in the same manner as in Example 1. The amounts of polyacrylic acid and copper sulfate supported on the activated carbon mixed paper were 40000 μg and 32000 μg per 1 g of the activated carbon mixed paper.
＜実施例９＞
次に、実施例１において、１．０質量％のポリアクリル酸（平均分子量５０００）を１．０質量％のポリアクリル酸（平均分子量１００００）とした以外は、実施例１と同様にして消臭フィルターを得た。なお、ポリアクリル酸の活性炭混抄紙への担持量は、活性炭混抄紙１ｇ当り５０００μｇであった。ポリカルボン酸の分子量が大きくなると、乾燥後に成膜性が大きくなるため活性炭の細孔や金属フタロシアニン錯体を覆うことから、消臭性能の低下はあるものの合格であった。
<Example 9>
Next, in Example 1, except that 1.0% by mass of polyacrylic acid (average molecular weight 5000) was changed to 1.0% by mass of polyacrylic acid (average molecular weight 10,000), the same procedure as in Example 1 was followed. An odor filter was obtained. The amount of polyacrylic acid supported on the activated carbon mixed paper was 5000 μg per 1 g of the activated carbon mixed paper. When the molecular weight of the polycarboxylic acid is increased, the film-forming property is increased after drying, so that the pores of the activated carbon and the metal phthalocyanine complex are covered.
＜実施例１０＞
実施例１で得られた消臭フィルター２枚を重ねて消臭フィルターとし、各種ガスの消臭試験をおこない除去率を表に記載した。
<Example 10>
Two deodorizing filters obtained in Example 1 were stacked to form a deodorizing filter, and various gases were deodorized and the removal rates were listed in the table.
＜比較例１＞
実施例１において、椰子殻活性炭を含まない天然パルプのみの水スラリーを作成した以外は、実施例１と同様にして、消臭フィルターを得た。上記の各種ガスの消臭試験をおこない除去率を表に記載した。
<Comparative Example 1>
In Example 1, a deodorizing filter was obtained in the same manner as in Example 1 except that an aqueous slurry containing only natural pulp containing no coconut shell activated carbon was prepared. The above-mentioned various gases were deodorized and the removal rates were listed in the table.
＜比較例２＞
実施例１において、金属フタロシアニン錯体の担持量を０とした以外は実施例１と同様にして、消臭フィルターを得た。
<Comparative example 2>
In Example 1, a deodorizing filter was obtained in the same manner as in Example 1 except that the supported amount of the metal phthalocyanine complex was 0.
＜比較例３＞
実施例１において、ポリアクリル酸（平均分子量５０００）の活性炭混抄紙への担持量を０とした以外は実施例１と同様にして、消臭フィルターを得た。
<Comparative Example 3>
In Example 1, a deodorizing filter was obtained in the same manner as in Example 1 except that the amount of polyacrylic acid (average molecular weight 5000) supported on the activated carbon mixed paper was 0.
＜比較例４＞
実施例１において、硫酸銅の活性炭混抄紙への担持量を０とした以外は実施例１と同様にして、消臭フィルターを得た。
<Comparative example 4>
In Example 1, a deodorizing filter was obtained in the same manner as in Example 1 except that the amount of copper sulfate supported on the activated carbon mixed paper was 0.
＜比較例５＞
実施例１において、椰子殻活性炭３０質量部と天然パルプ７０質量部を水２００質量部に添加し、水スラリーを作成した以外は実施例１と同様にして、消臭フィルターを得た。活性炭混抄紙における椰子殻活性炭の含有率は３０質量％であった。
<Comparative Example 5>
In Example 1, a deodorizing filter was obtained in the same manner as in Example 1 except that 30 parts by mass of coconut shell activated carbon and 70 parts by mass of natural pulp were added to 200 parts by mass of water to prepare a water slurry. The content of coconut shell activated carbon in the activated carbon mixed paper was 30% by mass.
＜比較例６＞
実施例１において、椰子殻活性炭８５質量部と天然パルプ１５質量部を水２００質量部に添加し、水スラリーを作成した以外は実施例１と同様にして、活性炭混抄紙を得たが、紙として強度がなく、活性炭の脱落も多くフィルターの形態にならなかった。
<Comparative Example 6>
In Example 1, activated carbon mixed paper was obtained in the same manner as in Example 1 except that 85 parts by mass of coconut shell activated carbon and 15 parts by mass of natural pulp were added to 200 parts by mass of water to prepare a water slurry. As a result, there was no strength and there was a lot of falling off of the activated carbon, so it did not form a filter.
＜比較例７＞
実施例１において、カチオン化処理を行わずに０．５質量％のコバルトフタロシアニンポリスルホン酸ナトリウム水溶液に含浸した以外は実施例１と同様にして、消臭フィルターを得た。コバルトフタロシアニンポリスルホン酸ナトリウムの活性炭混抄紙への担持量は、活性炭混抄紙１ｇ当り３０μｇであった。
<Comparative Example 7>
In Example 1, a deodorizing filter was obtained in the same manner as in Example 1 except that it was impregnated with 0.5% by mass of an aqueous solution of sodium cobalt phthalocyanine polysulfonate without performing cationization treatment. The amount of sodium cobalt phthalocyanine polysulfonate supported on the activated carbon mixed paper was 30 μg per 1 g of the activated carbon mixed paper.
＜比較例８＞
実施例１において、１．０質量％のポリアクリル酸（平均分子量２５０００）と１．０質量％の硫酸銅の水溶液に含浸した以外は実施例１と同様にして、消臭フィルターを得た。
<Comparative Example 8>
In Example 1, a deodorizing filter was obtained in the same manner as in Example 1 except that it was impregnated with an aqueous solution of 1.0% by mass of polyacrylic acid (average molecular weight 25000) and 1.0% by mass of copper sulfate.
＜比較例９＞
実施例１において、５．０質量％のポリアクリル酸（平均分子量５０００）と２．０質量％の硫酸銅の水溶液に含浸し、水洗を行わずに乾燥した以外は実施例１と同様にして、消臭フィルターを得た。ポリアクリル酸と硫酸銅の活性炭混抄紙への担持量は、活性炭混抄紙１ｇ当り８００００μｇと５５０００μｇであった。ポリアクリル酸の担持量が多すぎると、活性炭の細孔を塞いでしまうことから、二硫化ジメチルの消臭性能の低下がみられた。
<Comparative Example 9>
Example 1 is the same as Example 1 except that it is impregnated with an aqueous solution of 5.0% by mass of polyacrylic acid (average molecular weight 5000) and 2.0% by mass of copper sulfate, and dried without washing. A deodorant filter was obtained. The amounts of polyacrylic acid and copper sulfate supported on the activated carbon mixed paper were 80000 μg and 55000 μg per 1 g of the activated carbon mixed paper. When the amount of polyacrylic acid supported was too large, pores of the activated carbon were blocked, and thus the deodorizing performance of dimethyl disulfide was reduced.
表１から分かるように、活性炭混抄紙に金属フタロシアニン錯体と、ポリカルボン酸と、二価の銅又は亜鉛の塩を担持させた消臭フィルターは、塩基性ガスと酸性ガスの両方を素早く吸着除去することができ、また、表２から分かるように、活性炭、金属フタロシアニン錯体、ポリカルボン酸、二価の銅の塩のいずれか一つの欠けるものでは、消臭能力の劣るものであり、またポリアクリル酸の分子量の大きな比較例８や、ポリアクリル酸の担持量の多い比較例９も消臭能力の劣るものであった。
As can be seen from Table 1, a metal phthalocyanine complex on activated carbon mixed paper, a polycarboxylic acid, deodorizing filter obtained by supporting a salt of divalent copper or zinc, rapidly adsorb and remove both basic gas and acidic gas it can be, also, as can be seen from Table 2, the activated carbon, metal phthalocyanine complexes, polycarboxylic acids, intended to lack of any one of the divalent copper salt are those poor deodorizing capability, also poly Comparative Example 8 having a large molecular weight of acrylic acid and Comparative Example 9 having a large amount of polyacrylic acid were also inferior in deodorizing ability.
本発明の技術は、家庭用または業務用の冷蔵庫内の脱臭フィルター材、あるいはトイレや生ゴミ処理機等のいやな臭を取り除くフィルター材として広く利用される。 The technology of the present invention is widely used as a deodorizing filter material in a refrigerator for home use or business use, or a filter material for removing unpleasant odors such as toilets and garbage processing machines.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011160853A (en) * | 2010-02-05 | 2011-08-25 | Suminoe Textile Co Ltd | Deodorizing device |
| JP2012063046A (en) * | 2010-09-14 | 2012-03-29 | Suminoe Textile Co Ltd | Small air cleaner including human body detection sensor |
| JP5885917B2 (en) * | 2010-10-29 | 2016-03-16 | ダイワボウホールディングス株式会社 | Antibacterial deodorant, its fiber structure, and medical / nursing care products |
| KR101813030B1 (en) * | 2010-12-29 | 2017-12-28 | 엘지전자 주식회사 | Refrigerator |
| JP2014050416A (en) * | 2012-09-04 | 2014-03-20 | Suminoe Textile Co Ltd | Flame-retardant deodorant filter |
| JP6066176B2 (en) * | 2012-12-06 | 2017-01-25 | 住江織物株式会社 | Cigarette odor deodorant filter |
| JP2017088697A (en) * | 2015-11-06 | 2017-05-25 | 真庭バイオケミカル株式会社 | Modified cellulose fiber |
| CN106984362A (en) * | 2017-04-27 | 2017-07-28 | 重庆紫光化工股份有限公司 | Activated carbon supported Tetrasulphated phthalcyanine cobalt and its application as catalyst in dimethyl disulfide is prepared |
| CN106984361B (en) * | 2017-04-27 | 2020-02-18 | 重庆紫光化工股份有限公司 | Activated carbon-loaded cobalt tetraaminophthalocyanine and application thereof as catalyst in preparation of dimethyl disulfide |
| KR101923458B1 (en) * | 2017-12-19 | 2018-11-29 | 엘지전자 주식회사 | Refrigerator |
| CN112423716A (en) * | 2018-05-25 | 2021-02-26 | 国际纸业公司 | Odor-controlling absorbent materials and absorbent articles, and related methods of use and methods of manufacture |
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| JPS53133590A (en) * | 1977-04-27 | 1978-11-21 | Mitsubishi Electric Corp | Deodorizing-air purifying filter |
| JPS627000A (en) * | 1985-02-06 | 1987-01-13 | 大和紡績株式会社 | Deodorizing wet nonwoven fabric |
| JPS63137935A (en) * | 1986-11-28 | 1988-06-09 | Panatsuku Kogyo Kk | Freshness-keeping film |
| JPH01288318A (en) * | 1988-05-17 | 1989-11-20 | Nippon Carbide Ind Co Inc | Novel deodorization filter |
| JPH0623024A (en) * | 1992-05-11 | 1994-02-01 | Mitsubishi Electric Corp | Deodorizing material |
| JP3605694B2 (en) * | 1995-05-22 | 2004-12-22 | 東洋紡績株式会社 | Antibacterial / deodorant / water-absorbing textile products and method for producing the same |
| JPH09173248A (en) * | 1995-12-27 | 1997-07-08 | Daiwabo Co Ltd | Deodorant mat for toilet |
| JPH114878A (en) * | 1997-06-18 | 1999-01-12 | Daiwabo Co Ltd | Deodorant |
| JP4938164B2 (en) * | 1999-04-30 | 2012-05-23 | 株式会社クレハ | Deodorant structure and deodorant |
| TW200514586A (en) * | 2003-10-20 | 2005-05-01 | Suminoe Textile | Deodorizing filter material |
| JP2006280487A (en) * | 2005-03-31 | 2006-10-19 | Suminoe Textile Co Ltd | Deodorizing filter |
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