Deodorant composition and deodorizing filter

Abstract

To provide a deodorant composition which contains activated carbon and is excellent in terms of capturing efficiency and storage stability.SOLUTION: A deodorant composition contains activated carbon on which various aminooxyalkyl group-containing polysiloxanes are supported. (In the formula, each R independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and the alkyl group may be substituted with a primary amino group at any position; each Q independently represents -CH2-, -CH2CH2- or the like; and n represents a real number of 0 to 100).SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] 2. Description of the Related Art Deodorizing compositions and deodorizing filters containing activated carbon have been used as methods for removing malodorous gases.

[0003] Activated carbon deodorizes by absorbing odor molecules, but there is a limit to how much it can absorb, so when the amount absorbed is saturated, the odor molecules absorbed by the activated carbon are released again. Also, activated carbon alone is insufficient in deodorizing the odor of aldehyde-based gases, which are malodorous gases.

[0004] Therefore, the removal of malodorous gases using activated carbon carrying an aldehyde scavenger that captures aldehydes through a chemical reaction has been studied. As the aldehyde scavenger, those made of hydrazine derivatives, amines, amino acids, urea derivatives, etc. are known (see, for example, Patent Documents 1 to 4). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 11-299878 [Patent Document 2] JP 2000-300652 A [Patent Document 3] JP 2007-215818 A [Patent Document 4] JP 2018-108360 A Summary of the Invention [Problem to be solved by the invention]

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

[0007] The present invention has been made in view of the background of the conventional technology, and has an object to provide a deodorizing composition that exhibits excellent aldehyde capturing effect and maintains its capturing performance even after long-term storage in the air. [Means for solving the problem]

[0008] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that a composition containing activated carbon carrying a specific polysiloxane, which will be described later, can solve the above-mentioned problems, and have thus completed the present invention.

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

[0010] [1] A deodorant composition comprising activated carbon carrying an aminooxyalkyl group-containing polysiloxane having a structural unit represented by the following general formula (1):

[0011] [ka]

[0012] [In the formula, each R independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and the alkyl group may be substituted with a primary amino group at any position. Each Q independently represents one or more groups selected from the group consisting of -CH2-, -CH2CH2-, and -CH2-Ra-CH2-. Ra represents an alkylene group having 1 to 18 carbon atoms, and two or more non-adjacent -CH2- in the alkylene group may each independently be replaced with -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-, and a hydrogen atom in the alkylene group may be substituted with an alkyl group having 1 to 3 carbon atoms. n represents a real number of 0 to 100.] [2] The deodorant composition according to the above [1], wherein in the aminooxyalkyl group-containing polysiloxane represented by the general formula (1), each R is independently a methyl group, a 3-aminopropyl group, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, or a hydroxyl group.

[0013] [3] The deodorant composition according to the above [1] or [2], wherein in the aminooxyalkyl group-containing polysiloxane represented by the general formula (1), n ​​is 0.

[0014] [4] The deodorant composition according to any one of the above [1] to [3], wherein the amount of the aminooxyalkyl group-containing polysiloxane represented by the general formula (1) supported on the activated carbon is 0.1 to 100% by weight.

[0015] [5] A deodorizing filter comprising the deodorizing composition according to any one of [1] to [4] above.

[0016] [6] The deodorizing filter according to the above item [5], wherein the content of the deodorizing composition is 1 to 90% by weight of the deodorizing filter.

[0017] [7] A method for removing aldehyde, comprising contacting the deodorant composition according to any one of [1] to [4] above with an aldehyde-containing gas.

[0018] [8] A method for removing aldehyde, comprising contacting the deodorizing filter according to [5] or [6] above with an aldehyde-containing gas. Effect of the Invention

[0019] The deodorant composition of the present disclosure can capture aldehydes quickly and continuously, and as a result, is effective in reducing aldehydes that are harmful to the human body, and has the effect of improving the living environment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The deodorizing composition and deodorizing filter according to one embodiment of the present disclosure will be described in detail below. In this specification, the symbol "to" means a numerical range including both ends of the symbol.

[0021] In the present disclosure, the deodorant composition contains activated carbon carrying an aminooxyalkyl group-containing polysiloxane having a structural unit represented by the above general formula (1).

[0022] In the above general formula (1), each R independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and the alkyl group may be substituted with a primary amino group at any position.

[0023] The alkyl group having 1 to 4 carbon atoms is not particularly limited, but 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, and a tert-butyl group.

[0024] The alkoxy group having 1 to 4 carbon atoms is not particularly limited, but 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, and a tert-butoxy group.

[0025] Among these, R is preferably a methyl group, a 3-aminopropyl group, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, or a hydroxyl group because of its excellent aldehyde scavenging performance.

[0026] Each Q independently represents one or more groups selected from the group consisting of -CH2-, -CH2CH2-, and -CH2-Ra-CH2-.

[0027] Ra represents an alkylene group having 1 to 18 carbon atoms, in which two or more non-adjacent -CH2- groups may each independently be replaced by -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-, and a hydrogen atom of the alkylene group may be substituted by an alkyl group having 1 to 3 carbon atoms.

[0028] Q is not particularly limited, but specific examples include structures represented by the following chemical formulas (Q-1) to (Q-95), etc.

[0029] [ka]

[0030] [ka]

[0031] In the chemical formulas (Q-1) to (Q-95), the hydrogen atom on the alkylene group may be substituted with an alkyl group having 1 to 3 carbon atoms. * represents the bonding position in the general formula (1).

[0032] The alkyl group having 1 to 3 carbon atoms is not particularly limited, but examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

[0033] In the above general formula (1), n ​​represents a real number of 0 to 100. n is preferably 0 to 10 in that aldehyde trapping performance is excellent.

[0034] The amount of the aminooxyalkyl group-containing polysiloxane represented by the above general formula (1) supported on the activated carbon is not particularly limited, but is, for example, preferably 0.1 to 100% by weight, more preferably 5 to 100% by weight, and even more preferably 40 to 100% by weight.

[0035] The molecular shape of the aminooxy group-containing polysiloxane represented by the above general formula (1) is not particularly limited, and it can have any molecular shape, for example, a straight chain, branched chain, cyclic, or the like.

[0036] In the present disclosure, the deodorant composition contains an aminooxyalkyl group-containing polysiloxane having a structural unit represented by the above general formula (1) and activated carbon, and may further contain an acid, a base, a binder, a thickener, a defoamer, a surfactant, an antibacterial agent, a preservative, etc.

[0037] 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, phosphoric acid, etc., and organic acids such as acetic acid, citric acid, fumaric acid, maleic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, benzoic acid, p-toluenesulfonic acid, malonic acid, barbituric acid, 1,3-dimethylbarbituric acid, Meldrum's acid, etc. As the acid, hydrochloric acid, sulfuric acid, phosphoric acid, and barbituric acid are more preferable in terms of excellent aldehyde scavenging performance.

[0038] The base is not particularly limited, but 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, and cesium hydrogen carbonate; lithium citrate, sodium citrate, potassium citrate, rubidium citrate, cesium citrate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, and trifluoromethanesulfonate. Examples of organic bases include rubidium phosphate, cesium trifluoromethanesulfonate, polyethyleneimine, ethanolamine, diethanolamine, triethanolamine, trishydroxymethylaminomethane, ethylenediamine, diethylenetriamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, ethylenediamine-N,N,N',N'-tetraethanol, 1,4-piperazinediethanol, 1-(2,3-dihydroxypropyl)piperazine, 2-hydroxymethyltriethylenediamine, piperazine, and N-(2-aminoethyl)piperazine. As the base, ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium trifluoromethanesulfonate, and trishydroxymethylaminomethane are more preferable in terms of excellent aldehyde scavenging performance.

[0039] In the present disclosure, when the deodorant contains the above-mentioned acid or base, the content of the acid or base is not particularly limited, but is preferably in the range of 0.001 to 10 molar equivalents, more preferably in the range of 0.005 to 5 molar equivalents, and more preferably in the range of 0.01 to 2 molar equivalents, relative to 1 mole of the group represented by -ONH2.

[0040] The surfactant is not particularly limited, but examples thereof include anionic surfactants such as linear alkylbenzene sulfonate, alkyl ether sulfate, and polyoxyethylene alkyl ether carboxylate, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, and polyoxyalkylene alkylamine, amphoteric surfactants such as alkylamino fatty acid salt, alkyl betaine, and alkylamine oxide, and cationic surfactants such as alkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, ester-type dialkyl ammonium salt, and amide-type alkyl ammonium salt. Among these, linear alkylbenzene sulfonate is more preferred in terms of excellent aldehyde capture performance, and specific examples thereof include sodium decylbenzene sulfonate, sodium undecylbenzene sulfonate, sodium dodecylbenzene sulfonate, sodium tridecylbenzene sulfonate, sodium tetradecylbenzene sulfonate, sodium pentadecylbenzene sulfonate, sodium hexadecylbenzene sulfonate, sodium heptadecylbenzene sulfonate, and sodium octadecylbenzene sulfonate.

[0041] In the present disclosure, when the deodorant composition contains the binder, thickener, defoamer, surfactant, antibacterial agent, or preservative, the amount of the binder, thickener, defoamer, surfactant, antibacterial agent, or preservative supported on the activated carbon is not particularly limited, but each independently is preferably in the range of 0.01 to 100% by weight, more preferably in the range of 0.01 to 30% by weight, and more preferably in the range of 0.01 to 10% by weight.

[0042] In the present disclosure, the deodorant composition includes an aminooxyalkyl group-containing polysiloxane represented by the above general formula (1) supported on activated carbon.

[0043] In the present disclosure, the method for producing the deodorant composition is not particularly limited, but examples thereof include a method of applying a solution of the aminooxyalkyl group-containing polysiloxane represented by the above general formula (1) (hereinafter referred to as the polysiloxane solution) to activated carbon, and a method of immersing activated carbon in the polysiloxane solution.

[0044] The solvent for the polysiloxane solution is not particularly limited, but examples thereof include water, methanol, ethanol, toluene, etc. Among these, water is preferred because it is inexpensive and harmless to the human body.

[0045] After the aminooxyalkyl group-containing polysiloxane represented by the general formula (1) is supported on the activated carbon, it may be dried as necessary. The drying conditions can be adjusted as desired depending on the purpose and are not particularly limited, but for example, the temperature is in the range of 0 to 200°C and the time is in the range of several minutes to 48 hours.

[0046] In the present disclosure, the deodorant composition can be used by being incorporated into industrial products.

[0047] The industrial products mentioned above refer to industrial products and raw materials that have been widely known in the past, and are not particularly limited, but include, for example, paints, adhesives, inks, sealants, paper products, binders, resin emulsions, pulp, wood materials, wood products, plastic products, films, wallpapers, building materials (gypsum boards, interior materials, ceiling materials, floor materials, etc.), textile products, filters, etc. Examples of filters include deodorizing filters such as deodorizing filters for air purifiers and cabin air filters. In addition, composite materials of these are also included in the industrial products. Examples of composite materials include composite materials of wood and plastic, etc.

[0048] When a filter (particularly a deodorizing filter) is used as an industrial product, a conventionally known structure can be adopted as the structure.

[0049] In the present disclosure, aldehyde can be removed by contacting the above-mentioned deodorant composition with an aldehyde-containing gas.

[0050] In addition, in the present disclosure, aldehyde can be removed by contacting the above-mentioned deodorizing filter with an aldehyde-containing gas. [Brief description of the drawings]

[0051] [Figure 1] 1 shows mass spectrometry data obtained by measuring the molecular weight of the aminooxyalkyl group-containing polysiloxane obtained in Synthesis Example 9 using a mass spectrometer (microTOF, manufactured by Bruker Daltonics). [Diagram 2] FIG. 1 is a schematic diagram of an aldehyde trapping test device used in Examples 28 to 29 and Comparative Examples 12 to 13. EXAMPLES

[0052] The present embodiment will be described in more detail below with reference to examples, but these are merely examples to aid in the understanding of the present invention, and the present invention is not limited by these examples in any way. Unless otherwise specified, the reagents and the like used are commercially available products.

[0053] The following abbreviations are used for the compounds used in the examples.

[0054] O-[3-(triethoxysilyl)propyl]hydroxylamine:Si-1 3-(Triethoxysilyl)propylamine: Si-2 3-(diethoxymethylsilyl)propylamine: Si-3 Tetraethoxysilane: TEOS Triethoxymethylsilane:TEMS Diethoxydimethylsilane: DEDMS

[0055] [ka]

[0056] <Synthesis Example 1> Si-1 (0.78 g, 3.29 mmol) was mixed with water (9.22 g) and stirred under reflux conditions (oil bath temperature 110°C) for 20 hours to obtain a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the obtained aminooxyalkyl group-containing polysiloxane was measured using a gel filtration permeation chromatograph (Shimadzu Corporation, Prominence), and the number average molecular weight (Mn) was 930, the weight average molecular weight (Mw) was 1100, and the dispersity (Mw / Mn) was 1.18.

[0057] <Synthesis Example 2> A reaction was carried out in the same manner as in Synthesis Example 1, except that Si-1 (2.00 g, 8.43 mmol) and water (8.00 g) were mixed, to obtain a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the obtained aminooxyalkyl group-containing polysiloxane was measured in the same manner as in Synthesis Example 1, and the results were Mn=940, Mw=990, and Mw / Mn=1.05.

[0058] <Synthesis Example 3> Si-1 (0.78 g, 3.29 mmol) and water (9.22 g) were mixed and stirred under reflux conditions (oil bath temperature 110° C.) for 20 hours, and then allowed to stand at 60° C. for 14 days to obtain a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the obtained aminooxyalkyl group-containing polysiloxane was measured in the same manner as in Synthesis Example 1, and the results were Mn=1100, Mw=1300, and Mw / Mn=1.18.

[0059] <Synthesis Example 4> A reaction was carried out in the same manner as in Synthesis Example 1, except that Si-1 (0.78 g, 3.29 mmol), 1 mol / L hydrochloric acid (3.29 g, 3.29 mmol), and water (5.93 g) were mixed, to obtain a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the obtained aminooxyalkyl group-containing polysiloxane was measured in the same manner as in Synthesis Example 1, and the results were Mn=890, Mw=910, and Mw / Mn=1.02.

[0060] <Synthesis Example 5> A reaction was carried out in the same manner as in Synthesis Example 1, except that Si-1 (0.78 g, 3.29 mmol), 1 mol / L sulfuric acid (0.33 g, 0.33 mmol), and water (8.89 g) were mixed, to obtain a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the obtained aminooxyalkyl group-containing polysiloxane was measured in the same manner as in Synthesis Example 1, and the results were Mn=1400, Mw=1700, and Mw / Mn=1.21.

[0061] <Synthesis Example 6> A reaction was carried out in the same manner as in Synthesis Example 1, except that Si-1 (0.78 g, 3.29 mmol), 14.6 mol / L phosphoric acid (0.02 g, 0.33 mmol), and water (9.20 g) were mixed, to obtain a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the obtained aminooxyalkyl group-containing polysiloxane was measured in the same manner as in Synthesis Example 1, and the results were Mn=1200, Mw=1200, and Mw / Mn=1.00.

[0062] <Synthesis Example 7> A reaction was carried out in the same manner as in Synthesis Example 1, except that Si-1 (0.78 g, 3.29 mmol), Si-2 (0.08 g, 0.33 mmol), and water (9.15 g) were mixed, to obtain a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the obtained aminooxyalkyl group-containing polysiloxane was measured in the same manner as in Synthesis Example 1, and the results were Mn=890, Mw=920, and Mw / Mn=1.03.

[0063] <Synthesis Example 8> A reaction was carried out in the same manner as in Synthesis Example 1, except that Si-1 (0.78 g, 3.29 mmol), Si-3 (0.97 g, 3.29 mmol), and water (8.25 g) were mixed, to obtain a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the obtained aminooxyalkyl group-containing polysiloxane was measured in the same manner as in Synthesis Example 1, and the results were Mn=1200, Mw=1600, and Mw / Mn=1.33.

[0064] <Synthesis Example 9> A reaction was carried out in the same manner as in Synthesis Example 1, except that Si-1 (0.78 g, 3.29 mmol), TEOS (0.21 g, 1.01 mmol), and water (9.01 g) were mixed, to obtain a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the obtained aminooxyalkyl group-containing polysiloxane was measured in the same manner as in Synthesis Example 1, and the results were Mn=1000, Mw=1200, and Mw / Mn=1.20.

[0065] <Synthesis Example 10> A reaction was carried out in the same manner as in Synthesis Example 1, except that Si-1 (0.78 g, 3.29 mmol), TEMS (1.0 g, 3.29 mmol), and water (8.22 g) were mixed, to obtain a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the obtained aminooxyalkyl group-containing polysiloxane was measured in the same manner as in Synthesis Example 1, and the results were Mn=2100, Mw=3900, and Mw / Mn=1.86.

[0066] <Synthesis Example 11> A reaction was carried out in the same manner as in Synthesis Example 1, except that Si-1 (0.78 g, 3.29 mmol), DEDMS (1.3 g, 3.29 mmol), and water (7.92 g) were mixed, to obtain a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the obtained aminooxyalkyl group-containing polysiloxane was measured in the same manner as in Synthesis Example 1, and the results were Mn=1700, Mw=2500, and Mw / Mn=1.47.

[0067] <Synthesis Example 12> A reaction was carried out in the same manner as in Synthesis Example 1, except that Si-2 (0.73 g, 3.29 mmol) and water (9.27 g) were mixed, to obtain a transparent solution containing an aminoalkyl group-containing polysiloxane. The molecular weight of the obtained aminoalkyl group-containing polysiloxane was measured in the same manner as in Synthesis Example 1, and the results were Mn=750, Mw=770, and Mw / Mn=1.02.

[0068] Table 1 shows the raw material compositions of the polysiloxane solutions prepared in Synthesis Examples 1 to 12 and the molecular weights of the polysiloxanes.

[0069] [Table 1]

[0070] Example 1 <Preparation of Deodorant Composition> 0.3 g of the polysiloxane solution obtained in Synthesis Example 1 (hereinafter referred to as the supporting solution) was dropped onto 0.3 g of activated carbon (Shirasagi KL, activated carbon mesh 10-60, manufactured by Osaka Gas Chemicals) and dried at 90°C for 3 hours using a hot air dryer (DRJ433DA, manufactured by Advantec Co., Ltd.) to obtain a deodorant composition supporting polysiloxane containing aminooxyalkyl groups.

[0071] <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 on a cartridge carrying 2,4-dinitrophenylhydrazine (DNPH) (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. The eluate was then subjected to a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation) to quantify the acetaldehyde concentration. Furthermore, the acetaldehyde capture rate was calculated from the following formula.

[0072] Acetaldehyde capture rate [%] = [(initial acetaldehyde concentration - residual acetaldehyde concentration) ÷ initial acetaldehyde concentration] × 100.

[0073] Example 2 In Example 2, a deodorizing composition was prepared in the same manner as in Example 1, except that the activated carbon was changed to Shirasagi G2x (activated carbon mesh 4-6) manufactured by Osaka Gas Chemicals, and an aldehyde capture test was carried out.

[0074] Examples 3 to 12 In Examples 3 to 12, deodorant compositions were prepared in the same manner as in Example 1, except that the carrier liquid used in Example 1 was changed to a polysiloxane solution having the composition shown in Table 2 (prepared in Synthesis Examples 2 to 11), and an aldehyde capture test was carried out.

[0075] Comparative Examples 1-2 In Comparative Examples 1 and 2, the same procedures as in Example 1 were carried out, except that the deodorant composition was changed to activated carbon that had not been subjected to the dropping and drying operations of the polysiloxane solution (Comparative Example 1: Shirasagi KL, Comparative Example 2: Shirasagi G2x), and the aldehyde capture rate was measured.

[0076] Comparative Example 3 In Comparative Example 3, a deodorant composition was prepared in the same manner as in Example 1, except that the carrier liquid used in Example 1 was changed to the polysiloxane solution prepared in Synthesis Example 12, and an aldehyde capture test was carried out.

[0077] The results of Examples 1 to 12 and Comparative Examples 1 to 3 are shown in Table 2. As is clear from Table 2, the deodorant composition according to the present disclosure exhibited superior aldehyde trapping performance compared to the case of using only activated carbon. Also, compared to the case of supporting polysiloxane not containing an aminooxyalkyl group in its structure (Comparative Example 3), it exhibited superior aldehyde trapping performance.

[0078] [Table 2]

[0079] Example 13 <Preparation of deodorizing filter> 2g of the supporting solution was added with 6g of 50vol% aqueous solution of ethanol to obtain a 4-fold diluted solution. 0.43mL of this 4-fold diluted solution was dropped onto an activated carbon-containing nonwoven fabric filter (UES UF-APN) cut into 5cm squares, and then dried at 60°C for 30 minutes using a hot air dryer (Advantec DRJ433DA) to obtain a deodorizing filter supporting the aminooxyalkyl group-containing polysiloxane. Furthermore, the amount of the aminooxyalkyl group-containing polysiloxane supported on the activated carbon and the amount of activated carbon in the filter were calculated from the following formulas, respectively.

[0080] Supported amount [wt%] = (amount of diluted solution dropped [mL] × density of diluted solution [g / mL] ÷ dilution rate of polysiloxane solution) / (catalog value of activated carbon content in filter [g / m 2 ]×0.0025[m 2 ]) x 100.

[0081] Activated carbon content in the filter [wt%] = Catalog value of activated carbon content in the filter [g / m2] / Filter mass [g / m 2 ]×100.

[0082] <Acetaldehyde capture test> The 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) (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. The eluate was then subjected to a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation) to quantify the acetaldehyde concentration. Furthermore, the acetaldehyde capture rate was calculated from the following formula.

[0083] Acetaldehyde capture rate [%] = [(initial acetaldehyde concentration - residual acetaldehyde concentration) ÷ initial acetaldehyde concentration] × 100.

[0084] Examples 14-15 In Examples 14 and 15, the deodorizing filter used in Example 13 was changed to a UES activated carbon-containing nonwoven fabric filter UF-APM in Example 14, and to a UES activated carbon-containing urethane filter UF-PU3 in Example 15. Except for this, deodorizing compositions were prepared in the same manner as in Example 13, and the acetaldehyde capture rates were measured.

[0085] Comparative Examples 4 to 6 In Comparative Example 4, the activated carbon-containing nonwoven filter UF-APN was used, in Comparative Example 5, the activated carbon-containing nonwoven filter UF-APM was used, and in Comparative Example 6, the activated carbon-containing urethane filter UF-PU3 was used. In all of these cases, the dripping of the support liquid and the drying operation were not performed, and an acetaldehyde capture test was carried out in the same manner as in Example 13.

[0086] The results of Examples 13 to 15 and Comparative Examples 4 to 6 are shown in Table 3. 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.

[0087] [Table 3]

[0088] Example 16 <Preparation of deodorizing filter> 1 mol / L hydrochloric acid (0.66 g, 0.66 mmol) and water (5.34 g) were added to 2 g of the supporting solution to obtain a 4-fold diluted solution. 0.39 mL of this 4-fold diluted 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 Co., Ltd.) to obtain a deodorizing filter supporting the aminooxyalkyl group-containing polysiloxane. Furthermore, the amount of the aminooxyalkyl group-containing polysiloxane supported on the activated carbon and the activated carbon content in the filter were calculated from the following formulas, respectively.

[0089] Supported amount [wt%] = (amount of diluted solution dropped [mL] × density of diluted solution [g / mL] ÷ dilution rate of polysiloxane solution) / (catalog value of activated carbon content in filter [g / m 2 ]×0.0025[m 2 ]) x 100.

[0090] Activated carbon content in the filter [wt%] = Catalog value of activated carbon content in the filter [g / m2] / Filter mass [g / m 2 ]×100.

[0091] <Acetaldehyde capture test> The 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) (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. The eluate was then subjected to a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation) to quantify the acetaldehyde concentration. Furthermore, the acetaldehyde capture rate was calculated from the following formula.

[0092] Acetaldehyde capture rate [%] = [(initial acetaldehyde concentration - residual acetaldehyde concentration) ÷ initial acetaldehyde concentration] × 100.

[0093] Examples 17 to 23 In Examples 17 to 23, deodorant compositions were prepared in the same manner as in Example 16, except that the dilution liquid used in Example 16 was changed to a 4-fold diluted solution of a polysiloxane solution having the composition shown in Table 4, and the acetaldehyde capture rate was measured.

[0094] The results of Examples 16 to 23 are shown in Table 4. As is clear from Table 4, the deodorant composition according to the present disclosure exhibits excellent aldehyde capturing performance even when it contains an acid, a base, and a surfactant.

[0095] [Table 4]

[0096] Example 24 <Preparation of Deodorant Composition> 0.3 g of the supporting liquid was dropped onto 0.3 g of activated carbon (Shirasagi C2c, activated carbon mesh 20-48, manufactured by Osaka Gas Chemicals) and dried at 60°C for 6 hours using a hot air dryer (DRJ433DA, manufactured by Advantec Co., Ltd.) to obtain a deodorizing composition supporting polysiloxane containing aminooxyalkyl groups.

[0097] <Acetaldehyde capture test> 0.25g of the deodorant composition was sealed in a 10L Tedlar bag, and then 5L of nitrogen gas with an acetaldehyde concentration of 1ppm was added to the Tedlar bag. After standing at room temperature for 4 hours, the gas in the Tedlar bag was adsorbed on a cartridge carrying 2,4-dinitrophenylhydrazine (DNPH) (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. The eluate was then subjected to a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation) to quantify the acetaldehyde concentration. Furthermore, the acetaldehyde capture rate was calculated from the following formula.

[0098] Acetaldehyde capture rate [%] = [(initial acetaldehyde concentration - residual acetaldehyde concentration) ÷ initial acetaldehyde concentration] × 100.

[0099] Furthermore, the deodorant composition in the Tedlar bag was collected and stored in an air atmosphere at room temperature for 3 months. After 3 months, the collected composition was again sealed in a 10 L Tedlar bag and the acetaldehyde capture test was carried out in the same manner.

[0100] Example 25 In Example 25, a deodorant composition was prepared by the same procedure as in Example 24, except that the carrier liquid used in Example 24 was changed to the polysiloxane solution prepared in Synthesis Example 9, and an aldehyde capture test was carried out.

[0101] Comparative Example 7 In Comparative Example 7, a deodorant composition was prepared in the same manner as in Example 24, except that the carrier liquid used in Example 24 was changed to a 3% aqueous solution of a compound represented by the following formula (2) (referred to as aminooxyacetic acid in Table 5), and an aldehyde capture test was carried out.

[0102] [ka]

[0103] The results of Examples 24 to 25 and Comparative Example 7 are shown in Table 5.

[0104] [Table 5]

[0105] As is clear from Table 5, the deodorant composition according to the present disclosure maintains its aldehyde trapping performance even when stored for a long period of time in an air atmosphere, compared to deodorant compositions carrying a conventionally known aldehyde trapping agent.

[0106] Example 26 <Preparation of deodorizing filter> 16g of water was added to 1g of the supporting liquid to obtain a 17-fold diluted solution. Two sheets of activated carbon-containing nonwoven fabric filters (UES, UF-APM) cut into 5cm squares were prepared, each of which was immersed in the aforementioned diluted solution, and then passed through a press (Imoto Manufacturing, IMC-6600) to be pressed. Furthermore, using a hot air dryer (Advantec, DRJ433DA), one sheet was dried at 60°C for 30 minutes, and the other sheet was dried at 130°C for 1 hour, to obtain a total of two deodorizing filters with different heating and drying conditions. Furthermore, the amount of deodorant supported on the activated carbon and the activated carbon content in the filter were calculated from the following formulas, respectively.

[0107] Loading amount [wt%] = (filter mass after squeezing [g] - filter mass before immersion [g]) ÷ dilution rate of polysiloxane solution) / (catalog value of activated carbon content in filter [g / m 2 ]×0.0025[m 2 ]) x 100. Activated carbon content in the filter [wt%] = Catalog value of activated carbon content in the filter [g / m 2 ] / filter mass [g / m 2 ] x 100 <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 bag. After standing at room temperature for 1 hour, the gas in each Tedlar bag was adsorbed onto a cartridge carrying 2,4-dinitrophenylhydrazine (DNPH) (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. The eluate was then quantified for acetaldehyde concentration using a liquid chromatograph (Shimadzu Corporation, LC-2030C Plus). Furthermore, the acetaldehyde capture rate was calculated from the following formula.

[0108] Acetaldehyde capture rate [%] = [(initial acetaldehyde concentration - residual acetaldehyde concentration) ÷ initial acetaldehyde concentration] × 100.

[0109] Example 27 In Example 27, a deodorant composition was prepared in the same manner as in Example 26, except that the carrier liquid used in Example 26 was changed to the polysiloxane solution prepared in Synthesis Example 9, and an aldehyde capture test was carried out.

[0110] Comparative Example 8 In Comparative Example 8, two activated carbon-containing nonwoven fabric filters (UF-APM manufactured by UES) cut into 5 cm squares were prepared, one of which was dried for 30 minutes at 60° C. and the other for 1 hour at 130° C. An aldehyde capture test was carried out in the same manner as in Example 26, except that these filters were used as deodorizing filters.

[0111] Comparative Example 9 In Comparative Example 9, a deodorizing filter was prepared in the same manner as in Example 26, except that the support liquid used in Example 26 was changed to a 3% aqueous solution of the compound represented by the above formula (2), and an acetaldehyde capture test was carried out.

[0112] Comparative Example 10 In Comparative Example 10, a deodorizing filter was prepared in the same manner as in Example 26, except that the support liquid used in Example 26 was changed to a 3% aqueous solution of adipic acid dihydrazide (a product of Tokyo Chemical Industry Co., Ltd.), and an acetaldehyde capture test was carried out.

[0113] Comparative Example 11 In Comparative Example 11, a deodorizing filter was prepared in the same manner as in Example 26, except that the support liquid used in Example 26 was changed to a 3% aqueous solution of 4-amino-1,2,4-triazole (a product of Tokyo Chemical Industry Co., Ltd.), and an acetaldehyde capture test was carried out.

[0114] The results of Examples 26 to 27 and Comparative Examples 8 to 11 are shown in Table 6. As is clear from Table 6, the deodorizing filter of the present invention maintains its aldehyde trapping performance even when heated and dried at a high temperature, compared to deodorizing filters carrying a conventionally known aldehyde trapping agent.

[0115] [Table 6]

[0116] Example 28 <Preparation of deodorizing filter> 16 g of water was added to 1 g of the polysiloxane solution (hereinafter referred to as the supporting solution) prepared in Synthesis Example 1 to obtain a 17-fold diluted solution. Three sheets of activated carbon-containing nonwoven fabric filters (UF-APM manufactured by UES) cut into 6 cm squares were prepared and immersed in the above-mentioned diluted solution, and then passed through a press (IMC-6600 manufactured by Imoto Manufacturing Co., Ltd.) to be pressed. Furthermore, three deodorizing filters supporting the aminooxyalkyl group-containing polysiloxane were obtained by drying for 30 minutes at 60°C using a hot air dryer (DRJ433DA manufactured by Advantec Co., Ltd.). Furthermore, the amount of deodorant supported on the activated carbon was calculated from the following formula.

[0117] Loading amount [wt%] = (filter mass after squeezing [g] - filter mass before immersion [g]) × deodorant concentration in diluted solution [%] / (catalog value of activated carbon content in filter [g / m 2 ]×0.0025[m 2 ]) x 100.

[0118] <Acetaldehyde capture test> One of the deodorizing filters is connected to a SUS pipe (flow sectional area 13 cm 2 ) perpendicular to the flow path so as to completely cover the flow path. One end of the piping 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 (Shibata Scientific, MP-Σ300NII), and the air in the sealed container was reduced in pressure by the power of the suction pump, causing the gas in the 100 L Tedlar bag to pass through the filter and be collected in the 5 L Tedlar bag. An overview of the device is shown in Figure 2.

[0119] 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 set to 0.5 L / min (0.007 m / sec) to collect 3 L of aldehyde gas. The collected gas was adsorbed onto a cartridge carrying 2,4-dinitrophenylhydrazine (DNPH) (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. The acetaldehyde concentration of the eluate was then quantified using a liquid chromatograph (Shimadzu Corporation, LC-2030C Plus). Furthermore, the acetaldehyde capture rate was calculated from the following formula.

[0120] Acetaldehyde capture rate [%] = [(initial acetaldehyde concentration - residual acetaldehyde concentration) ÷ initial acetaldehyde concentration] × 100.

[0121] Next, the suction pump was changed to an LV-40BW manufactured by Shibata Scientific, and of the remaining deodorant compositions, the flow rate of one sheet was changed to 14 L / min (0.18 m / sec) and the other to 40 L / min (0.53 m / sec). Except for this, acetaldehyde gas was captured using the same procedures as above, and the aldehyde capture rate was measured.

[0122] Example 29 In Example 29, a deodorizing filter was prepared in the same manner as in Example 28, except that the supporting liquid used in Example 28 was changed to the polysiloxane solution prepared in Synthesis Example 9, and an acetaldehyde capture test was carried out.

[0123] Comparative Example 12 In Comparative Example 12, an aldehyde capture test was carried out in the same manner as in Example 28, except that an activated carbon-containing nonwoven fabric filter (UF-APM manufactured by UES) cut into a 6 cm square was used as a deodorizing filter without being subjected to a loading operation.

[0124] Comparative Example 13 In Comparative Example 13, a deodorizing filter was prepared in the same manner as in Example 28, except that the support liquid used in Example 28 was changed to a 40% aqueous solution of 4-amino-1,2,4-triazole (a product of Tokyo Chemical Industry Co., Ltd.), and an acetaldehyde capture test was carried out.

[0125] The results of Examples 28 to 29 and Comparative Examples 12 to 13 are shown in Table 7. As is clear from Table 7, the deodorizing filter of the present invention has an advantage that the capture rate is less likely to decrease even when the flow rate of acetaldehyde gas is increased, compared to deodorizing filters carrying a conventionally known aldehyde scavenger.

[0126] [Table 7] [Explanation of symbols]

[0127] 1 100L Tedlar Bag 2 Flange with filter 3 5L Tedlar Bag 4 10L airtight container 5. Suction pump

Claims

1. A deodorant composition comprising activated carbon carrying an aminooxyalkyl group-containing polysiloxane having a structural unit represented by the following general formula (1): 【Chemistry 1】 [In the formula, each R independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and the alkyl group may be substituted with a primary amino group at any position. Each Q independently represents -CH ２ --, --CH ２ CH ２ - and -CH ２ -Ra-CH ２ Ra represents an alkylene group having 1 to 18 carbon atoms, and in the alkylene group, two or more non-adjacent —CH ２ Each - may be independently replaced by -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-, and a hydrogen atom of the alkylene group may be replaced by an alkyl group having 1 to 3 carbon atoms. n represents a real number of 0 to 100.]

2. The deodorant composition according to claim 1, wherein in the aminooxyalkyl group-containing polysiloxane represented by the general formula (1), each R is independently a methyl group, a 3-aminopropyl group, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, or a hydroxyl group.

3. 2. The deodorant composition according to claim 1, wherein n is 0 in the aminooxyalkyl group-containing polysiloxane represented by the general formula (1).

4. 2. The deodorant composition according to claim 1, wherein the amount of the aminooxyalkyl group-containing polysiloxane represented by the general formula (1) supported on the activated carbon is 0.1 to 100% by weight.

5. A deodorizing filter comprising the deodorizing composition according to any one of claims 1 to 4.

6. 6. The deodorizing filter according to claim 5, wherein the content of the deodorizing composition is 1 to 90% by weight of the deodorizing filter.

7. A method for removing aldehyde, comprising contacting the deodorant composition according to any one of claims 1 to 4 with an aldehyde-containing gas.

8. A method for removing aldehyde, comprising contacting the deodorizing filter according to claim 5 or 6 with an aldehyde-containing gas.

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