Deodorizing composition and deodorization filter

Abstract

To provide a deodorizing composition containing activated carbon, exhibiting superior capture efficiency and storage stability.SOLUTION: A deodorizing composition comprises a supported carrier having at least one structure among structures represented by the following general formula (1), and activated carbon. [In the general formula (1), R represents an alkyl group having 1 to 4 carbon atoms; X represents an alkoxy group having 1 to 4 carbon atoms; m represents an integer of 0 to 2; m' represents 0 or 1; and n represents an integer of 1 to 12. When m is 2, the plurality of R groups may be the same or different. When m is 0, the plurality of X groups may be the same or different.]SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a deodorant composition and a deodorizing filter.

Background Art

[0002] Conventionally, as a method for removing malodorous gases, a deodorant composition containing activated carbon and a deodorizing filter have been used.

[0003] Activated carbon deodorizes by adsorbing odor molecules, but since there is a limit to the adsorption amount, when the adsorption amount becomes saturated, the odor molecules adsorbed on the activated carbon are desorbed and re-released. Also, for aldehyde-based gases among malodorous gases, the deodorizing performance is insufficient with only activated carbon.

[0004] Therefore, the removal of malodorous gases using activated carbon supporting an aldehyde scavenger that captures aldehydes by a chemical reaction has been studied. As the above-mentioned aldehyde scavenger, those composed of hydrazine derivatives, amines, amino acids, urea derivatives, etc. are known (for example, see Patent Documents 1 to 4).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, when the aldehyde scavengers described in these patent documents are supported on activated carbon, the scavenging efficiency is not always sufficient, and there is also a problem that the scavenging performance deteriorates rapidly over time.

[0007] An object of the present disclosure is to provide a deodorizing composition that exhibits an excellent scavenging effect on aldehydes and maintains its scavenging performance even after being stored in air for a long period of time.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a specific carrier and activated carbon described below can solve the above problems, and have completed the present invention.

[0009] That is, the present disclosure includes the embodiments shown below.

[0010] [1] A deodorizing composition comprising a carrier having an aminooxyalkyl group supported by a chemical bond and having a structural unit represented by the following general formula (1), and activated carbon.

[0011]

Chemical Formula

[0012] [In the above general formula (1), R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. m represents an integer of 0 to 2. m' represents 0 or 1. n represents an integer of 1 to 12. When m is 2, a plurality of Rs may be the same or different. When m is 0, a plurality of Xs may be the same or different.] [2] The deodorizing composition according to the above [1], wherein in the general formula (1), R is a methyl group and X is each independently a methoxy group, an ethoxy group, an isopropoxy group, or a hydroxyl group.

[0013] [3] The deodorant composition according to the above [1] or [2], wherein the carrier is silica gel, alumina, zeolite, magnesia, titania, zirconia, ceria, diatomaceous earth, activated carbon, cellulose, or hydroxyapatite.

[0014] [4] The deodorant composition according to the above [1] or [2], wherein the carrier is silica gel.

[0015] [5] Further, the deodorant composition according to any one of the above [1] to [4], comprising at least one binder resin selected from the group consisting of an acrylate resin, a silicone resin, and a urethane resin.

[0016] [6] A deodorant filter comprising the deodorant composition according to any one of the above [1] to [5].

[0017] [7] The deodorant filter according to the above [6], wherein the content of the deodorant composition is 1 to 90% by weight of the deodorant filter.

[0018] [8] A method for removing aldehydes, which comprises bringing the deodorant composition according to any one of the above [1] to [5] into contact with an aldehyde-containing gas.

[0019] [9] A method for removing aldehydes, which comprises bringing the deodorant filter according to the above [6] or [7] into contact with an aldehyde-containing gas.

Advantages of the Invention

[0020] The deodorant composition of the present disclosure can rapidly and continuously capture aldehydes. As a result, it is effective in reducing aldehydes harmful to the human body and has the effect of improving the living environment.

Modes for Carrying Out the Invention

[0021] Hereinafter, the deodorant composition and the deodorant filter according to one aspect of the present disclosure will be described in detail.

[0022] In the present disclosure, the deodorant composition includes a carrier having an aminooxyalkyl group supported by a chemical bond and having a structural unit represented by the above general formula (1) (hereinafter referred to as "supported carrier"), and activated carbon.

[0023] In the above general formula (1), R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. m represents an integer of 0 to 2. m' represents 0 or 1. n represents an integer of 1 to 12. When m is 2, the plurality of Rs may be the same or different. When m is 0, the plurality of Xs may be the same or different.

[0024] The alkyl group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 3-aminopropyl group, a butyl group, a 2-methylpropyl group, a 1-methylpropyl group, or a tert-butyl group.

[0025] The alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a 2-methylpropyloxy group, a 1-methylpropyloxy group, or a tert-butoxy group.

[0026] Among these, R is preferably a methyl group or a 3-aminopropyl group in terms of excellent aldehyde capture performance, and X is preferably a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, or a hydroxyl group.

[0027] m is an integer of 0 to 2. Also, when m is 2, the plurality of Rs may be the same or different, and when m is 0, the plurality of Xs may be the same or different. m is preferably 0 in terms of excellent aldehyde capture performance.

[0028] m' is an integer of 0 or 1. m' is preferably 0 in terms of excellent aldehyde capture performance.

[0029] n is an integer from 1 to 12, and although not particularly limited, examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, etc.

[0030] Among these, from the viewpoint of excellent aldehyde scavenging performance, a propylene group, a butylene group, or a pentylene group is preferable, and a propylene group is more preferable.

[0031] In the present disclosure, in the supported carrier, part or all of the aminooxyalkyl group may be a chemically acceptable salt with an inorganic acid or an organic acid. The type of the salt is not particularly limited, and examples thereof include inorganic acid salts such as hydrochloride, hydrobromide, perchlorate, silicate, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate, and phosphate, or organic acid salts such as acetate, citrate, fumarate, maleate, trifluoromethanesulfonate, trifluoroacetate, benzoate, and p-toluenesulfonate. Inorganic acid salts are preferable in terms of low cost, and hydrochloride is more preferable.

[0032] The amount of the aminooxyalkyl group supported on the carrier can be arbitrarily adjusted according to the purpose, and although not particularly limited, a range of 0.01 to 10 mmol / g of the aminooxyalkyl group relative to the carrier weight is preferable.

[0033] As the carrier, any water-insoluble material can be used without particular limitation. For example, as the polymer carrier, styrene-based polymers such as polystyrene and crosslinked polystyrene, polyolefins such as polyethylene and polypropylene, poly(halogenated olefins) such as polyvinyl chloride and polytetrafluoroethylene, nitrile-based polymers such as polyacrylonitrile, (meth)acrylic-based polymers such as polymethyl methacrylate and polyethyl acrylate, high molecular weight polysaccharides such as cellulose, agarose, and dextran can be mentioned. As the inorganic carrier, silica gel, alumina, zeolite, magnesia, titania, zirconia, ceria, diatomaceous earth, activated carbon, cellulose, hydroxyapatite, etc. can be mentioned. As the carrier to be mixed with the silane coupling agent, an inorganic carrier is preferable and silica gel is more preferable in terms of the efficiency of the silane coupling reaction. The above-mentioned silane coupling reaction refers to a reaction in which a siloxane bond is formed between the silane coupling agent and the carrier by a dehydration or dealcoholization reaction, etc.

[0034] The shape of the carrier is not particularly limited. For example, generally used shapes as separation substrates such as spherical (e.g., spherical particles, etc.), granular, fibrous, particulate, monolithic column, hollow fiber, membrane-like (e.g., flat membrane, etc.) can be used. Among these, spherical, membrane-like, granular, particulate, or fibrous ones are preferable. Spherical, granular, or particulate carriers are particularly preferably used because their use volume can be freely set when used in column methods or batch methods. As the particle size of the spherical, granular, or particulate carrier, usually, those in the range of an average particle diameter of 0.1 μm to 10 mm can be used, but it is preferably 1 μm to 100 μm in terms of good dispersibility in a liquid.

[0035] The carrier may be porous or non-porous. As the average pore diameter of the porous carrier, usually, those in the range of 1 nm to 1 μm can be used, but the range of 1 nm to 300 nm is preferable in terms of the deodorization rate.

[0036] In the present disclosure, the deodorant composition contains the above-mentioned supported carrier and activated carbon, but may further contain a binder resin, an acid, a base, a thickener, an antifoaming agent, a surfactant, an antibacterial agent, a preservative, and the like.

[0037] In the present disclosure, the binder resin contained in the deodorant composition is not particularly limited, and examples thereof include acrylic ester resins, silicone resins, urethane resins, polyester resins, melamine resins, polypropylene resins, and fluororesins. Among these, acrylic ester resins, silicone resins, or urethane resins are preferred because of their excellent adhesion to the substrate and water resistance.

[0038] The acid is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, hydrobromic acid, perchloric acid, silicic acid, tetrafluoroboric acid, hexafluorophosphoric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acid salts such as acetic acid, citric acid, fumaric acid, maleic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, benzoic acid, and p-toluenesulfonic acid. As the acid, inorganic acids are preferred in terms of low cost, and hydrochlorides, sulfuric acid, and phosphoric acid are more preferred.

[0039] The base is not particularly limited, and examples thereof include inorganic bases such as ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, lithium citrate, sodium citrate, potassium citrate, rubidium citrate, cesium citrate, and organic bases such as polyethyleneimine, ethanolamine, diethanolamine, triethanolamine, tris(hydroxymethyl)aminomethane, ethylenediamine, diethylenetriamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, ethylenediamine-N,N,N’,N’-tetraethanol, 1,4-piperazinediethano, 1-(2,3-dihydroxypropyl)piperazine, 2-hydroxymethyltriethylenediamine, piperazine, N-(2-aminoethyl)piperazine. As the base, an inorganic base is preferable in terms of low cost, and ammonia, sodium hydroxide, and potassium hydroxide are more preferable.

[0040] In the present disclosure, when the acid or base is contained in the deodorant deodorant, the content of the acid or base is not particularly limited, but -ONH 2 The range of 0.001 to 10 molar equivalents is preferable, the range of 0.005 to 5 molar equivalents is more preferable, and the range of 0.01 to 2 molar equivalents is more preferable with respect to 1 mole of the group represented by.

[0041] In the present disclosure, the method for producing the deodorant composition is not particularly limited. For example, a binder resin and a solvent are added to a carrier having an aminooxyalkyl group supported by a chemical bond or a chemically acceptable salt thereof represented by the above general formula (1), and stirred to obtain a binder liquid, and the binder liquid is applied to activated carbon. Examples thereof include a method of immersing activated carbon in the binder liquid.

[0042] In the present disclosure, the method of using the deodorant composition is not particularly limited, and examples thereof include a method of immobilizing on a substrate, applying, spraying and using, a method of spraying on an odor source, and the like.

[0043] In the present disclosure, when the binder resin, thickener, defoamer, surfactant, antibacterial agent, or preservative is included in the deodorant composition, the loading amount of the binder resin, thickener, defoamer, surfactant, antibacterial agent, or preservative on the activated carbon is not particularly limited, but each independently preferably ranges from 0.01 to 100% by weight, more preferably ranges from 0.01 to 30% by weight, and even more preferably ranges from 0.01 to 10% by weight.

[0044] In the present disclosure, the deodorant composition includes those in which the above-mentioned supported carrier is mixed with activated carbon, those supported on activated carbon, and the like.

[0045] In the present disclosure, the loading amount of the above-mentioned supported carrier on the activated carbon is not particularly limited, but for example, 0.1 to 100% by weight is preferred, 5 to 100% by weight is more preferred, and 10 to 50% by weight is even more preferred.

[0046] In the present disclosure, the deodorant composition may be immobilized on a substrate and used as a deodorant structure. The method of immobilizing the deodorant composition on the substrate is not particularly limited, and examples thereof include the method of applying the deodorant composition to the above-mentioned substrate, the method of immersing the above-mentioned substrate in the deodorant composition, and the like.

[0047] The immobilization amount of the deodorant composition on the substrate can be arbitrarily adjusted according to the purpose and is not particularly limited, but when the deodorant composition is 0.1 to 100 g / m 2 the range is preferred, and 5 to 20 g / m 2 the range is even more preferred.

[0048] In the present disclosure, after mixing the above-mentioned supported carrier with activated carbon, it may be dried as necessary. The drying conditions can be arbitrarily adjusted according to the purpose and are not particularly limited. For example, the temperature ranges from 0 to 200 °C and the time ranges from several minutes to 48 hours.

[0049] In the present disclosure, the deodorant composition can be used by being blended into industrial products.

[0050] The above-mentioned industrial products refer to industrially manufactured products and industrial raw materials that have been widely known conventionally, and are not particularly limited. For example, paints, adhesives, inks, sealing agents, paper products, binder resins, resin emulsions, pulp, wood materials, wood products, plastic products, films, wallpapers, building materials (such as gypsum boards, interior materials, ceiling materials, floor materials, etc.), fiber products, filters, etc. can be mentioned. Examples of the filter include deodorant filters such as deodorant filters for air purifiers and cabin air filters. In addition, these composite materials are also included in industrial products. Examples of the composite material include a composite material of wood and plastic.

[0051] When a filter (especially a deodorant filter) is adopted as an industrial product, a known structure known conventionally can be adopted as its structure.

[0052] In the present disclosure, aldehydes can be removed by bringing the above-mentioned deodorant composition into contact with an aldehyde-containing gas.

[0053] Also, in the present disclosure, aldehydes can be removed by bringing the above-mentioned deodorant filter into contact with an aldehyde-containing gas.

Brief Description of the Drawings

[0054]

Figure 1

Examples

[0055] The present embodiment will be described in more detail based on the following examples, which are examples for assisting the understanding of the present invention and the present invention is not limited by these examples in any way.

[0056] <Reagent> The following reagents and materials were used in the examples.

[0057] Silica gel: manufactured by Tosoh Silica Corporation, NIPGEL CX-400 Binder resin A: manufactured by Daiwa Chemical Industry Co., Ltd., Phicoat 70K (acrylate-based) Binder resin B: manufactured by Daiwa Chemical Industry Co., Ltd., Bindex S-200L (silicone-based) Binder resin C: manufactured by Daiwa Chemical Industry Co., Ltd., U-30NP (urethane-based) Activated carbon A: manufactured by Osaka Gas Chemical Co., Ltd., Shirasagi KL (activated carbon mesh 10 - 60) Activated carbon B: manufactured by Osaka Gas Chemical Co., Ltd., Shirasagi G2x (activated carbon mesh 4 - 6) Activated carbon filter A: manufactured by UES, activated carbon-containing non-woven fabric filter UF-APN (Activated carbon content in the filter: 36 wt%) Activated carbon filter B: manufactured by UES, activated carbon-containing non-woven fabric filter UF-APM (Activated carbon content in the filter: 83 wt%) Activated carbon filter C: manufactured by UES, activated carbon-containing urethane filter UF-PU3 (Activated carbon content in the filter: 41 wt%) Synthesis Example 1 19.94 g of silica gel and 173.4 g of toluene were put into a 500 mL beaker and mixed. The beaker was transferred into a nitrogen gas flow glove box, and a mixture of 8.08 g of the silane coupling agent represented by the following formula (1’) and 43.35 g of toluene was added dropwise over 30 minutes, and stirred at 25°C for 120 hours in that state.

[0058] The liquid component was removed from the obtained reaction solution by filtration, and the residue was dried at 120 °C for 4 hours to obtain a supported carrier. Elemental analysis of the obtained supported carrier revealed that the aminooxyalkyl group was contained at 1.4 mmol / g per unit mass of the supported carrier.

[0059]

Chem.

[0060] Example 1 <Preparation of Binder Solution> 25 g of the supported carrier obtained in Synthesis Example 1, 3 g of binder resin A, and 72 g of ion-exchanged water were placed in a bottle and mixed for adjustment. The dilution concentration was calculated from the following formula (1).

[0061]

Eq.

[0062] <Preparation of Deodorant Composition> 0.3 g of the above binder solution was dropped onto 0.3 g of activated carbon A, and dried at 90 °C for 3 hours using a hot air dryer (manufactured by Advantec, DRJ433DA) to obtain a deodorant composition in which the supported carrier was supported on the activated carbon. The amount of drug supported on the activated carbon was calculated from the following formula (2).

[0063]

Eq.

[0064] <Acetaldehyde Capture Test> 0.25 g of the above deodorant composition was sealed in a 10 L Tedlar bag, and then 5 L of nitrogen gas with an acetaldehyde concentration of 1 ppm was added to the Tedlar bag. After standing at room temperature for 2 hours, the gas in the Tedlar bag was adsorbed onto a cartridge (Presep-C DNPH, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) loaded with 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the concentration of acetaldehyde in the eluate was quantified using a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation). In addition, the acetaldehyde capture rate was calculated from the following formula (3).

[0065]

Equation

[0066] Example 2 A deodorant composition was prepared by performing the same operations as in Example 1, except that activated carbon A was changed to activated carbon B in the preparation of the deodorant composition, and an aldehyde capture test was carried out.

[0067] Example 3 A deodorant composition was prepared by performing the same operations as in Example 1, except that binder resin A was changed to ion-exchanged water when adjusting the binder solution, and an aldehyde capture test was carried out.

[0068] Example 4 A deodorant composition was prepared by performing the same operations as in Example 2, except that binder resin A was changed to ion-exchanged water when adjusting the binder solution, and an aldehyde capture test was carried out.

[0069] Comparative Example 1 The deodorant composition was subjected to the same operations as in Example 1, except that activated carbon A was changed, and the aldehyde capture rate was measured.

[0070] Comparative Example 2 The deodorant composition was subjected to the same operations as in Example 1, except that activated carbon B was changed, and the aldehyde capture rate was measured.

[0071] Comparative Example 3 The binder solution was prepared by putting 3 g of binder resin A and 72 g of ion-exchanged water into a bottle and mixing them. The same operations as in Example 1 were performed except for this, and the aldehyde capture rate was measured.

[0072] Comparative Example 4 The binder solution was prepared in the same manner as in Comparative Example 3. The same operations as in Example 2 were performed except for this, and the aldehyde capture rate was measured.

[0073] Comparative Example 5 In the preparation of the binder solution, a deodorant composition was prepared by performing the same operations as in Example 1 except that silica gel was used instead of the supported carrier obtained in Synthesis Example 1, and an aldehyde capture test was conducted.

[0074] Comparative Example 6 In the preparation of the binder solution, a deodorant composition was prepared by performing the same operations as in Example 2 except that silica gel was used instead of the supported carrier obtained in Synthesis Example 1, and an aldehyde capture test was conducted.

[0075] The results of Examples 1 to 4 and Comparative Examples 1 to 6 are shown in Table 1.

[0076]

Table 1

[0077] As is clear from Table 1, the deodorant composition according to the present disclosure exhibited excellent aldehyde capture performance as compared with the case of using only activated carbon. Further, it exhibited excellent aldehyde capture performance as compared with the case where silica gel not containing an aminooxyalkyl group in the structure was supported (Comparative Examples 5 and 6).

[0078] Example 5 <Adjustment of Binder Solution> 25 g of the supported carrier obtained in Synthesis Example 1, 3 g of binder resin, and 72 g of ion-exchanged water were put into a bottle and mixed for adjustment. The dilution concentration was calculated from the above formula (1).

[0079] <Preparation of Deodorant Composition (Without Washing)> 0.3 g of the binder solution was dropped onto 0.3 g of Activated Carbon A, and dried at 90 °C for 3 hours using a hot air dryer (manufactured by Advantec, DRJ433DA), thereby obtaining a deodorant composition in which the supported carrier was supported on activated carbon. Also, the amount of drug supported on the activated carbon was calculated from the above formula (2).

[0080] <Preparation of Deodorant Composition (With Washing)> 0.3 g of the binder solution was dropped onto 0.3 g of Activated Carbon A, and dried at 90 °C for 3 hours using a hot air dryer (manufactured by Advantec, DRJ433DA), thereby obtaining a deodorant composition in which the supported carrier was supported on activated carbon. Also, the amount of drug supported on the activated carbon was calculated from the above formula (2).

[0081] Subsequently, the adjusted deodorant composition was put into a beaker containing 5000 g of ion-exchanged water and stirred at 200 rpm for 30 minutes. Then, the solid obtained by vacuum filtration using a Nutsche and a suction flask was dried at 90 °C for 3 hours to obtain a deodorant composition (with washing).

[0082] <Acetaldehyde Capture Test> 0.25 g of the deodorant composition was sealed in a 10 L Tedlar bag, and then 5 L of nitrogen gas with an acetaldehyde concentration of 1 ppm was added to the Tedlar bag. After standing at room temperature for 2 hours, the gas in the Tedlar bag was adsorbed onto a cartridge (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Presep-C DNPH) loaded with 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the concentration of acetaldehyde in the eluate was quantified using a liquid chromatograph (manufactured by Shimadzu Corporation, LC-2030C Plus). Also, the acetaldehyde capture rate was calculated from the above formula (3).

[0083] Example 6 When preparing the deodorant composition, except for changing activated carbon A to activated carbon B, the same operations as in Example 1 were performed to prepare a deodorant composition (without water washing) and a deodorant composition (with water washing), and an aldehyde capture test was carried out.

[0084] Example 7 Except for changing the binder resin A used when adjusting the binder liquid to binder resin B, the same operations as in Example 5 were performed to prepare a deodorant composition, and an aldehyde capture test was carried out.

[0085] Example 8 When preparing the deodorant composition, except for changing activated carbon A to activated carbon B, the same operations as in Example 7 were performed to prepare a deodorant composition, and an aldehyde capture test was carried out.

[0086] Example 9 Except for changing the binder resin A used when adjusting the binder liquid to binder resin C, the same operations as in Example 5 were performed to prepare a deodorant composition, and an aldehyde capture test was carried out.

[0087] Example 10 When preparing the deodorant composition, except for changing activated carbon A to activated carbon B, the same operations as in Example 9 were performed to prepare a deodorant composition, and an aldehyde capture test was carried out.

[0088] The results of Examples 5 to 10 are shown together in Table 2.

[0089]

Table 2

[0090] As is clear from Table 2, the deodorant composition according to the present disclosure can be used in combination with various binder resins.

[0091] Example 11 <Adjustment of Binder Liquid> 20 g of the supported carrier obtained in Synthesis Example 1, 3 g of the binder resin, and 77 g of ion-exchanged water were mixed and adjusted. The dilution concentration was calculated from the above formula (1).

[0092] <Preparation of Deodorizing Filter> 0.25 g of the above binder solution was dropped onto an activated carbon filter A cut into a 5 cm square, and then dried at 60°C for 30 minutes using a hot air dryer (manufactured by Advantec, DRJ433DA) to obtain a deodorizing filter supporting the supported carrier. The amount of the supported carrier attached to the activated carbon was calculated from the following formula (4).

[0093]

Equation

[0094] <Preparation of Deodorizing Composition (with Water Washing)> 0.3 g of the above binder solution was dropped onto 0.3 g of activated carbon A and dried at 90°C for 3 hours using a hot air dryer (manufactured by Advantec, DRJ433DA) to obtain a deodorizing composition in which the supported carrier was supported on the activated carbon. The amount of the chemical attached to the activated carbon was calculated from the above formula (4). Subsequently, the adjusted deodorizing composition was put into a beaker containing 5000 g of ion-exchanged water and stirred at 200 rpm for 30 minutes. Then, the solid obtained by vacuum filtration using a Buchner funnel and an aspirator bottle was dried at 90°C for 3 hours to obtain a deodorizing composition (with washing).

[0095] <Acetaldehyde Capture Test> The deodorizing filter was enclosed in a 10 L Tedlar bag, and then 5 L of nitrogen gas with an acetaldehyde concentration of 10 ppm was added to the Tedlar bag. After standing at room temperature for 1 hour, the gas in the Tedlar bag was adsorbed onto a cartridge (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Corporation) loaded with 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the concentration of acetaldehyde in the eluate was quantified using a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation). In addition, the acetaldehyde capture rate was calculated from the above formula (3).

[0096] Examples 12 to 13 A deodorizing composition was prepared in the same manner as in Example 11, except that the activated carbon filter used in Example 11 was changed to activated carbon filter B in Example 12 and to activated carbon filter C in Example 14, and the acetaldehyde capture rate thereof was measured.

[0097] Example 14 A deodorizing composition was prepared in the same manner as in Example 11, except that the binder resin A of the binder liquid used in Example 11 was changed to ion-exchanged water, and the acetaldehyde capture rate thereof was measured.

[0098] Examples 15 to 16 A deodorizing composition was prepared in the same manner as in Example 14, except that the activated carbon filter used in Example 14 was changed to activated carbon filter B in Example 15 and to activated carbon filter C in Example 16, and the acetaldehyde capture rate thereof was measured.

[0099] Comparative Examples 7 to 9 Using only the activated carbon filter A in Comparative Example 7, only the activated carbon filter B in Comparative Example 8, and only the activated carbon filter C in Comparative Example 9 as the deodorizing filter, the capture rates of acetaldehyde were measured respectively.

[0100] Comparative Examples 10 to 12 In the preparation of the binder liquid, a deodorant composition was prepared by the same operations as in Examples 11 to 13 except that silica gel was used instead of the supported carrier obtained in Synthesis Example 1 and ion-exchanged water was used instead of the binder resin A to adjust the filter, and an acetaldehyde capture test was carried out by the same operations.

[0101] Comparative Examples 13 to 15 In the preparation of the binder liquid, a deodorant composition was prepared by the same operations as in Examples 11 to 13 except that silica gel was used instead of the supported carrier obtained in Synthesis Example 1 to adjust the filter, and an acetaldehyde capture test was carried out by the same operations.

[0102] The results of Examples 11 to 16 and Comparative Examples 7 to 15 are shown together in Table 3.

[0103]

Table 3

[0104] As is clear from Table 3, the deodorant composition according to the present disclosure has the effect of improving the aldehyde capture performance even when the activated carbon is fixed to the filter.

[0105] Example 17 <Preparation of Binder Liquid> 20 g of the supported carrier obtained in Synthesis Example 1, 3 g of binder resin A, and 77 g of ion-exchanged water were mixed and adjusted. The dilution concentration was calculated from the above formula (1).

[0106] <Preparation of Deodorizing Filter (Without Water Washing)> 0.25 g of the above binder liquid was dropped onto Activated carbon filter A and then dried at 60 °C for 30 minutes using a hot air dryer (manufactured by Advantec, DRJ433DA) to obtain a deodorizing filter carrying the supported carrier. The amount of the supported carrier attached to the activated carbon and the activated carbon content in the filter were calculated from the above formulas (4) and (5), respectively.

[0107] <Preparation of Deodorizing Filter (with Water Washing)> 0.25 g of the above binder solution was dropped onto an activated carbon-containing nonwoven fabric filter (UF-APN manufactured by UES) cut into a 5 cm square, and then dried at 60°C for 30 minutes using a hot air dryer (DRJ433DA manufactured by Advantec) to obtain a deodorizing filter carrying a carrier. This was put into a small washing machine (SY-135, manufactured by SOWI JAPAN) containing 5000 g of ion-exchanged water and stirred for 10 minutes in the washing mode. Subsequently, after dehydration for 5 minutes, it was dried at 60°C for 30 minutes to obtain a water-washed deodorizing filter (with water washing). Furthermore, the amount of deodorant attached to the activated carbon was calculated from the above formula (4).

[0108] <Acetaldehyde Capture Test> The above deodorizing filter was sealed in a 10 L Tedlar bag, and then 5 L of nitrogen gas with an acetaldehyde concentration of 10 ppm was added to the Tedlar bag. After standing at room temperature for 1 hour, the gas in the Tedlar bag was adsorbed onto a cartridge carrying 2,4-dinitrophenylhydrazine (DNPH) (Pressep-C DNPH manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the concentration of acetaldehyde in the eluate was quantified using a liquid chromatograph (LC-2030C Plus manufactured by Shimadzu Corporation). Also, the acetaldehyde capture rate was calculated from the above formula (3).

[0109] Examples 18 - 19 The activated carbon filter used in Example 17 was changed to activated carbon filter B in Example 18 and to activated carbon filter C in Example 19. Except for this change, a deodorizing composition was prepared by the same operation as in Example 17, and its acetaldehyde capture rate was measured.

[0110] Example 20 A deodorant composition was prepared in the same manner as in Example 17, except that the binder resin A used in Example 17 was changed to binder resin B, and the aldehyde capture rate thereof was measured.

[0111] Examples 21 to 22 The activated carbon filter used in Example 20 was changed to activated carbon filter B in Example 21, and to activated carbon filter C in Example 22. A deodorant composition was prepared in the same manner as in Example 21, except for the above changes, and the aldehyde capture rate thereof was measured.

[0112] Example 23 A deodorant composition was prepared in the same manner as in Example 17, except that the binder resin A used in Example 17 was changed to binder resin C, and the aldehyde capture rate thereof was measured.

[0113] Examples 24 to 25 The deodorant filter used in Example 23 was changed to activated carbon filter B in Example 24 and to activated carbon filter C in Example 25. A deodorant composition was prepared in the same manner as in Example 23, except for the above changes, and the aldehyde capture rate thereof was measured.

[0114] Comparative Examples 16 to 18 In Comparative Example 16, a deodorant composition was adjusted in the same manner as in Example 17, except that silica gel was used instead of the supported carrier obtained in Synthesis Example 1 in the preparation of the binder liquid, and the aldehyde capture rate thereof was measured.

[0115] In Comparative Examples 17 to 18, a deodorant composition was adjusted in the same manner as in Comparative Example 16, except that binder resin B was used in Comparative Example 17 and binder resin C was used in Comparative Example 18 instead of binder resin A in the preparation of the binder liquid, and the aldehyde capture rate thereof was measured.

[0116] The results of Examples 17 to 25 and Comparative Examples 16 to 18 are shown together in Table 4.

[0117]

Table 4

[0118] As is apparent from Table 4, the deodorant composition according to the present disclosure can further improve the washing durability when used in combination with a binder resin.

[0119] Example 26 <Adjustment of Binder Liquid> 3 g of the supported carrier obtained in Synthesis Example 1, 3 g of binder resin A, and 94 g of ion-exchanged water were mixed and adjusted. The dilution concentration was calculated from the above formula (1).

[0120] <Preparation of Deodorant Composition> 0.3 g of the above binder liquid was dropped onto 0.3 g of activated carbon A, and dried at 60 °C for 6 hours using a hot air dryer (manufactured by Advantec, DRJ433DA) to obtain a deodorant composition in which the supported carrier was supported on the activated carbon. The chemical loading amount of the activated carbon was calculated from the above formula (2).

[0121] <Acetaldehyde Capture Test> 0.25 g of the above deodorant composition was sealed in a 10 L Tedlar bag, and then 5 L of nitrogen gas with an acetaldehyde concentration of 1 ppm was added to the Tedlar bag. After standing at room temperature for 4 hours, the gas in the Tedlar bag was adsorbed onto a cartridge (manufactured by Fujifilm Wako Pure Chemical Corporation, Presep-C DNPH) loaded with 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the concentration of acetaldehyde in the eluate was quantified using a liquid chromatograph (manufactured by Shimadzu Corporation, LC-2030C Plus). The acetaldehyde capture rate was calculated from the above formula (3).

[0122] Furthermore, the deodorant composition in the Tedlar bag was recovered and stored at room temperature for 3 months in an air atmosphere. After 3 months, this recovered product was again sealed in a 10 L Tedlar bag, and an acetaldehyde capture test was carried out in the same manner.

[0123] Examples 27 to 28 In Examples 27 and 28, in the preparation of the binder liquid, except that the binder resin A was changed to binder resin B in Example 27 and to binder resin C in Example 28, the same operations as in Example 26 were carried out to prepare a deodorant composition, and an aldehyde capture test was conducted.

[0124] In Example 29, in the preparation of the binder liquid, except that the binder resin A was changed to 3 g of ion-exchanged water, the same operations as in Example 26 were carried out to prepare a deodorant composition, and an aldehyde capture test was conducted.

[0125] Comparative Example 19 A deodorant composition was prepared by performing the same operations as in Example 26, except that the binder liquid used in Example 26 was changed to a 3% aqueous solution of the compound represented by the following formula (3) (referred to as aminooxyacetic acid in Table 4), and an aldehyde capture test was conducted.

[0126]

Chemical formula

[0127] The results of Example 31 and Comparative Example 11 are shown together in Table 5.

[0128]

Table 5

[0129] As is clear from Table 5, the deodorant composition according to the present disclosure maintains its aldehyde capture performance even when stored in an air atmosphere for a long period of time, as compared with a deodorant composition carrying a conventionally known aldehyde scavenger.

[0130] Example 30 <Adjustment of binder liquid> 10 g of the supported carrier obtained in Synthesis Example 1, 9 g of binder resin A, and 281 g of water were mixed and adjusted. The dilution concentration was calculated from the above formula (1).

[0131] <Preparation of Deodorizing Filter> Two pieces of activated carbon filter A cut into squares with sides of 5 cm were prepared, each immersed in the aforementioned binder solution, and then passed through a press (manufactured by Imoto Seisakusho, IMC-6600) and squeezed. Further, using a hot air dryer (manufactured by Advantec, DRJ433DA), one piece was dried at 60 °C for 30 minutes and one piece was dried at 130 °C for 1 hour, thereby obtaining a total of two deodorizing filters with different heat drying conditions. Furthermore, the loading amount of the deodorant on the activated carbon was calculated from the above formula (4).

[0132] <Acetaldehyde Capture Test> The two deodorizing filters were each sealed in a 10 L Tedlar bag, and then 5 L of nitrogen gas with an acetaldehyde concentration of 10 ppm was sealed in each. After standing at room temperature for 1 hour, the gas in each Tedlar bag was adsorbed onto a cartridge (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Presep-C DNPH) carrying 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the concentration of acetaldehyde in the eluate was quantified using a liquid chromatograph (manufactured by Shimadzu Corporation, LC-2030C Plus). Furthermore, the acetaldehyde capture rate was calculated from the above formula (3).

[0133] Examples 31 to 33 In the preparation of the binder solution, except that binder resin A was changed to binder resin B in Example 31, binder resin C in Example 32, and ion-exchanged water in Example 33, deodorizing compositions were prepared by the same operations as in Example 30, and their acetaldehyde capture rates were measured.

[0134] Comparative Example 20 Two activated carbon filters A cut into squares with sides of 5 cm were prepared. An aldehyde capture test was conducted in the same manner as in Example 30, except that one filter dried at 60°C for 30 minutes and the other dried at 130°C for 1 hour were used as deodorizing filters.

[0135] Comparative Example 21 A deodorizing filter was produced by performing the same operations as in Example 30, except that a binder solution prepared from 10 g of a 3% aqueous solution of the compound represented by the above formula (3) and 40 g of water was used, and an acetaldehyde capture test was conducted.

[0136] Comparative Example 22 A deodorizing filter was produced by performing the same operations as in Example 30, except that a binder solution prepared from 10 g of a 3% aqueous solution of adipic acid dihydrazide (a product of Tokyo Chemical Industry) and 40 g of water was used, and an acetaldehyde capture test was conducted.

[0137] Comparative Example 23 A deodorizing filter was produced by performing the same operations as in Example 30, except that a binder solution prepared from 10 g of a 3% aqueous solution of 4-amino-1,2,4-triazole (a product of Tokyo Chemical Industry) and 40 g of water was used, and an acetaldehyde capture test was conducted.

[0138] The results of Examples 30 to 33 and Comparative Examples 20 to 23 are shown together in Table 6.

[0139]

Table 6

[0140] As is clear from Table 6, the deodorizing filter of the present invention maintains its aldehyde capture performance even when heated and dried at high temperatures, as compared with deodorizing filters carrying conventionally known aldehyde capture agents.

[0141] Example 34 <Adjustment of Binder Solution> 10 g of the supported carrier obtained in Synthesis Example 1, 9 g of binder resin A, and 281 g of water were mixed and adjusted. The dilution concentration was calculated from the above formula (1).

[0142] <Preparation of Deodorizing Filter> Two pieces of activated carbon filter A cut into 5 cm squares were prepared, each immersed in the above-mentioned binder solution, and then passed through a press (manufactured by Imoto Seisakusho, IMC-6600) and pressed. Further, using a hot air dryer (manufactured by Advantec, DRJ433DA), drying was carried out at 60 °C for 30 minutes to obtain a total of 2 deodorizing filters. One of these was put into a small washing machine (SY-135, manufactured by Sowi Japan) containing 5000 g of ion-exchanged water and stirred for 10 minutes in the washing mode. Subsequently, after dehydration for 5 minutes, it was dried at 60 °C for 30 minutes to obtain a washed deodorizing filter. Furthermore, the loading amount of the deodorant on the activated carbon was calculated from the above formula (4).

[0143] <Acetaldehyde Capture Test> The above two deodorizing filters were each sealed in a 10 L Tedlar bag, and then 5 L each of nitrogen gas with an acetaldehyde concentration of 10 ppm was sealed. After standing at room temperature for 1 hour, the gas in each Tedlar bag was adsorbed onto a cartridge (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Presep-C DNPH) carrying 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the concentration of acetaldehyde in the eluate was quantified using a liquid chromatograph (manufactured by Shimadzu Corporation, LC-2030C Plus). Furthermore, the acetaldehyde capture rate was calculated from the above formula (3).

[0144] Examples 35 to 36 In Examples 35 to 36, except that the binder resin A used when preparing the binder solution used in Example 34 was changed to binder resin B in Example 35 and binder resin C in Example 36, a deodorizing composition was prepared by the same operation as in Example 34, and its acetaldehyde capture rate was measured.

[0145] Example 37 A deodorant composition was prepared in the same manner as in Example 34, except that the binder resin A used when preparing the binder liquid used in Example 34 was changed to ion-exchanged water, and the acetaldehyde capture rate thereof was measured.

[0146] Comparative Example 24 A deodorant composition was prepared in the same manner as in Example 34, except that the activated carbon filter was used as it was without using the binder liquid used in Example 34, and the acetaldehyde capture rate thereof was measured.

[0147] Comparative Example 25 A deodorant filter was produced by performing the same operations as in Example 34, except that a binder liquid prepared from 10 g of a 3% aqueous solution of the compound represented by the above formula (3) and 40 g of water was used, and an acetaldehyde capture test was conducted.

[0148] Comparative Example 26 A deodorant filter was produced by performing the same operations as in Example 34, except that a binder liquid prepared from 10 g of a 3% aqueous solution of adipic acid dihydrazide (a product of Tokyo Chemical Industry) and 40 g of water was used, and an acetaldehyde capture test was conducted.

[0149] Comparative Example 27 A deodorant filter was produced by performing the same operations as in Example 34, except that a binder liquid prepared from 10 g of a 3% aqueous solution of 4-amino-1,2,4-triazole (a product of Tokyo Chemical Industry) and 40 g of water was used, and an acetaldehyde capture test was conducted.

[0150] The results of Examples 34 to 37 and Comparative Examples 24 to 27 are shown together in Table 7.

[0151]

Table 7

[0152] As is clear from Table 7, the deodorant composition according to the present disclosure can further improve the washing durability when used in combination with a binder resin.

[0153] Example 38 <Adjustment of Binder Liquid> 10 g of the supported carrier obtained in Synthesis Example 1, 9 g of binder resin A, and 281 g of water were mixed and prepared. The dilution concentration was calculated from the above formula (1).

[0154] <Preparation of Deodorant Filter> Three activated carbon filters A cut into squares with sides of 5 cm were prepared, immersed in the above-mentioned dilution solution, and then passed through a squeezing machine (IMC-6600 manufactured by Imoto Seisakusho) and squeezed. Further, using a hot air dryer (DRJ433DA manufactured by Advantec), drying was performed at 130 °C for 5 minutes to obtain three deodorant filters carrying the supported carrier. Furthermore, the loading amount of the deodorant on the activated carbon was calculated from the above formula (4).

[0155] <Acetaldehyde Capture Test> One of the above deodorant filters was attached perpendicularly to the flow path so as to completely cover the flow path at the flange portion of a SUS pipe (flow path cross-sectional area 13 cm 2 )). One end of the pipe was connected to a 100 L Tedlar bag, and the other end was connected to a sealed container containing a 5 L Tedlar bag. This sealed container was further connected to a suction pump (MP-Σ300NII manufactured by Shibata Scientific), and the air in the sealed container was decompressed by the power of the suction pump, so that the gas in the 100 L Tedlar bag passed through the filter and was collected in the 5 L Tedlar bag. The outline of the apparatus is shown in Figure 1.

[0156] 100 L of nitrogen gas with an acetaldehyde concentration of 4 ppm was sealed in a 100 L Tedlar bag, and the flow rate of the suction pump was 0.5 L / min (0.04 L / min / cm 2) was set, and 3 L of aldehyde gas was collected. The collected gas was adsorbed onto a cartridge (manufactured by Fuji Film Wako Pure Chemical Corporation, Presep-C DNPH) loaded with 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the concentration of acetaldehyde in the eluate was quantified using a liquid chromatograph (manufactured by Shimadzu Corporation, LC-2030C Plus). Furthermore, the acetaldehyde capture rate was calculated from the above formula (3).

[0157] Next, the suction pump was changed to LV-40BW manufactured by Shibata Scientific. Among the remaining deodorant compositions, for one sheet, the flow rate was changed to 14 L / min (1.1 L / min / cm 2 ), and for one sheet, the flow rate was changed to 40 L / min (3.2 L / min / cm 2 ). Except for this change, acetaldehyde gas was collected by the same operation as above, and the aldehyde capture rate was measured.

[0158] Comparative Example 28 An aldehyde capture test was conducted in the same manner as in Example 38, except that an activated carbon filter A cut into a 5 cm square was used as a deodorant filter without performing the adhering operation.

[0159] Comparative Example 29 A deodorant filter was prepared by performing the same operation as in Example 38, except that a binder solution prepared from 10 g of a 3% aqueous solution of the compound represented by the above formula (3) and 40 g of water was used, and an acetaldehyde capture test was conducted.

[0160] Comparative Example 30 A deodorant filter was prepared by performing the same operation as in Example 38, except that a binder solution prepared from 10 g of a 3% aqueous solution of adipic acid hydrazide and 40 g of water was used, and an acetaldehyde capture test was conducted.

[0161] Comparative Example 31 A deodorizing filter was prepared in the same manner as in Example 38 except that a binder solution prepared from 10 g of a 3% aqueous solution of 4-amino-1,2,4-triazole (a product of Tokyo Chemical Industry) and 40 g of water was used, and an acetaldehyde capture test was carried out.

[0162] The results of Example 38 and Comparative Examples 28 to 31 are shown together in Table 8.

[0163]

Table 8

[0164] As is clear from Table 8, the deodorizing filter of the present invention has the feature that the capture rate is less likely to decrease even when the flow rate of acetaldehyde gas is increased, as compared with a deodorizing filter carrying a conventionally known aldehyde scavenger.

Explanation of Symbols

[0165] 1 100L Tedlar bag 2 Flange with filter 3 5L Tedlar bag 4 10L sealed container 5 Suction pump

Claims

1. A deodorizing composition comprising a carrier carrying an aminooxyalkyl group by chemical bonding, the aminooxyalkyl group having at least one structure represented by the following general formula (1), and activated carbon: 【Chemistry 1】 [In the above general formula (1), R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. m represents an integer of 0 to 2. m' represents 0 or 1. n represents an integer of 1 to 12. When m is 2, multiple Rs may be the same or different. When m is 0, multiple Xs may be the same or different.]

2. 2. The deodorant composition according to claim 1, wherein in general formula (1), R is a methyl group, and each X is independently a methoxy group, an ethoxy group, an isopropoxy group, or a hydroxyl group.

3. 2. The deodorant composition according to claim 1, wherein the carrier is silica gel, alumina, zeolite, magnesia, titania, zirconia, ceria, diatomaceous earth, activated carbon, cellulose, or hydroxyapatite.

4. 2. The deodorant composition according to claim 1, wherein the carrier is silica gel.

5. 5. The deodorant composition according to claim 1, further comprising at least one binder resin selected from the group consisting of acrylic ester resins, silicone resins, and urethane resins.

6. A deodorizing filter comprising the deodorizing composition according to any one of claims 1 to 5.

7. 7. The deodorizing filter according to claim 6, wherein the content of the deodorizing composition is 1 to 90% by weight of the deodorizing filter.

8. A method for removing aldehyde, comprising contacting an aldehyde-containing gas with the deodorant composition according to any one of claims 1 to 5.

9. A method for removing aldehyde, comprising contacting the deodorizing filter according to claim 6 or 7 with an aldehyde-containing gas.

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