Deodorant composition and deodorizing filter

Abstract

Provided is a deodorant composition which contains activated carbon and is excellent in terms of capturing efficiency and storage stability.　The deodorant composition contains activated carbon on which an aminooxyalkyl group-containing polysiloxane having a structural unit represented by general formula (1) is 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 an arbitrary position; each Q independently represents one or more groups that are 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 -CH2- moieties that are not adjacent to each other in the alkylene group may be independently substituted by -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-, and the hydrogen atom in the alkylene group may be substituted by an alkyl group having 1 to 3 carbon atoms; and n represents a real number of 0 to 100.)

Description

Deodorizing composition and deodorizing filter

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

[0002] Conventionally, deodorizing compositions containing activated carbon and deodorizing filters have been used as methods for removing malodorous gases.

[0003] Activated carbon deodorizes by adsorbing odor molecules, but there is a limit to how much it can adsorb, and once the adsorption capacity is saturated, the odor molecules adsorbed on the activated carbon are released again. Furthermore, activated carbon alone is insufficient in deodorizing the odor of aldehyde-based gases, which are malodorous gases.

[0004] Therefore, studies have been conducted on the removal of malodorous gases using activated carbon loaded with an aldehyde scavenger that captures aldehydes through a chemical reaction. Known aldehyde scavengers include those made of hydrazine derivatives, amines, amino acids, urea derivatives, etc. (see, for example, Patent Documents 1 to 4).

[0005] Japanese Patent Application Publication No. 11-299878 Japanese Patent Application Publication No. 2000-300652 Japanese Patent Application Publication No. 2007-215818 Japanese Patent Application Publication No. 2018-108360

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

[0007] The present invention has been made in view of the background of the prior art, and aims to provide a deodorizing composition that exhibits an excellent aldehyde capturing effect and maintains its capturing performance even after being stored in the air for a long period of time.

[0008] As a result of intensive research into 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 following embodiments.

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

[0011]

[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 -CH ２ -, -CH ２ CH ２ - and -CH ２ -Ra-CH ２ Ra represents one or more groups selected from the group consisting of an alkylene group having 1 to 18 carbon atoms, and 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 substituted by an alkyl group having 1 to 3 carbon atoms. n represents a real number of 0 to 100.] [2] The deodorizing 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 n is 0 in the aminooxyalkyl group-containing polysiloxane represented by the general formula (1).

[0014] [4] The deodorizing 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 [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 deodorizing composition according to any one of the above [1] to [4] with an aldehyde-containing gas.

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

[0019] The deodorizing composition of the present disclosure can quickly and continuously capture aldehydes, which is effective in reducing aldehydes that are harmful to the human body and has the effect of improving living environments.

[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 inclusive of both the numerical values ​​at both ends.

[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 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 capturing performance.

[0026] Each Q is independently —CH ２ -, -CH ２ CH ２ - and -CH ２ -Ra-CH ２ - represents one or more groups selected from the group consisting of

[0027] Ra represents an alkylene group having 1 to 18 carbon atoms, and the alkylene group has two or more —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 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).

[0029]

[0030]

[0031] In the chemical formulas (Q-1) to (Q-95), a hydrogen atom on the alkylene group may be substituted with an alkyl group having 1 to 3 carbon atoms. * represents a 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. In terms of excellent aldehyde trapping performance, n is preferably 0 to 10.

[0034] The amount of the aminooxyalkyl group-containing polysiloxane represented by the general formula (1) supported on the activated carbon is not particularly limited, but is 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 general formula (1) is not particularly limited, and it can have any molecular shape, such as a straight chain, branched chain, or cyclic shape.

[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, an antifoaming agent, a surfactant, an antibacterial agent, an antiseptic, 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, and phosphoric acid, 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, and Meldrum's acid. As the acid, hydrochloric acid, sulfuric acid, phosphoric acid, and barbituric acid are more preferred in terms of their 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; 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 preferred 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 may be, for example, -ONH ２ The amount 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 still more preferably in the range of 0.01 to 2 molar equivalents, relative to 1 mole of the group represented by the formula:

[0040] The surfactant is not particularly limited, and examples thereof include anionic surfactants such as linear alkylbenzene sulfonates, alkyl ether sulfates, and polyoxyethylene alkyl ether carboxylates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyalkylene alkyl ethers, and polyoxyalkylene alkylamines; amphoteric surfactants such as alkylamino fatty acid salts, alkyl betaines, and alkylamine oxides; and cationic surfactants such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, ester-type dialkylammonium salts, and amide-type alkylammonium salts. Among these, linear alkylbenzene sulfonates are more preferred in terms of their excellent aldehyde-trapping performance, and specific examples thereof include sodium decylbenzenesulfonate, sodium undecylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium tridecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, sodium pentadecylbenzenesulfonate, sodium hexadecylbenzenesulfonate, sodium heptadecylbenzenesulfonate, and sodium octadecylbenzenesulfonate.

[0041] In the present disclosure, when the deodorant composition contains the binder, thickener, antifoaming agent, surfactant, antibacterial agent, or preservative, the amount of the binder, thickener, antifoaming agent, 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 an aminooxyalkyl group-containing polysiloxane represented by the above general formula (1) (hereinafter referred to as a polysiloxane solution) to activated carbon, and a method of immersing activated carbon in a 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 activated carbon, it may be dried, if necessary. The drying conditions can be adjusted arbitrarily 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 deodorizing composition can be incorporated into industrial products for use.

[0047] The industrial products referred to above refer to conventionally widely known industrial products and industrial raw materials, 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, wallpaper, building materials (gypsum board, 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. Furthermore, composite materials of these materials are also included in industrial products. Examples of composite materials include composite materials of wood and plastic.

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

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

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

[0051] 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). It is a schematic diagram of an aldehyde trapping test device used in Examples 28 to 29 and Comparative Examples 12 to 13.

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

[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]

[0056] Synthesis Example 1 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 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). The results were a number average molecular weight (Mn) of 930, a weight average molecular weight (Mw) of 1,100, and a polydispersity (Mw / Mn) of 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, yielding a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the resulting 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, yielding a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the resulting 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, yielding a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the resulting 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, yielding a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the resulting 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, yielding a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the resulting 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, yielding a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the resulting 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, yielding a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the resulting 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, yielding a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the resulting 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, yielding a transparent solution containing an aminooxyalkyl group-containing polysiloxane. The molecular weight of the resulting 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, yielding a transparent solution containing an aminoalkyl group-containing polysiloxane. The molecular weight of the resulting 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] The raw material compositions of the polysiloxane solutions prepared in Synthesis Examples 1 to 12 and the molecular weights of the polysiloxanes are shown in Table 1.

[0069]

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

[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 onto a cartridge (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) carrying 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the acetaldehyde concentration of the eluate was quantified using a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation). Furthermore, the acetaldehyde capture rate was calculated using 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 to 6) manufactured by Osaka Gas Chemicals, and an aldehyde capture test was carried out.

[0074] Examples 3 to 12 In Examples 3 to 12, deodorizing 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 and 2 In Comparative Examples 1 and 2, the same operations as in Example 1 were carried out, except that the deodorizing composition was changed to activated carbon to which the polysiloxane solution had not been added and dried (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 deodorizing 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 where activated carbon alone was used. Furthermore, superior aldehyde trapping performance was also shown compared to the case where polysiloxane not containing an aminooxyalkyl group in its structure was supported (Comparative Example 3).

[0078]

[0079] Example 13 <Preparation of Deodorizing Filter> 6 g of a 50 vol% aqueous solution of ethanol was added to 2 g of the supporting solution to obtain a 4-fold diluted solution. 0.43 mL of this 4-fold diluted solution was added dropwise to 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 an aminooxyalkyl group-containing polysiloxane. Furthermore, the amount of aminooxyalkyl group-containing polysiloxane supported relative to the activated carbon and the activated carbon content in the filter were each calculated using the following formulas.

[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] / Mass of the filter [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 (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) carrying 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the acetaldehyde concentration of the eluate was quantified using a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation). Furthermore, the acetaldehyde capture rate was calculated using the following formula:

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

[0084] Examples 14 to 15 In Examples 14 to 15, deodorizing compositions were prepared in the same manner as in Example 13, except that the deodorizing filter used in Example 13 was changed to an activated carbon-containing nonwoven fabric filter UF-APM manufactured by UES in Example 14, and to an activated carbon-containing urethane filter UF-PU3 manufactured by UES in Example 15, and the acetaldehyde capture rate thereof was measured.

[0085] Comparative Examples 4 to 6 An acetaldehyde capture test was carried out in the same manner as in Example 13, except that in Comparative Example 4, the activated carbon-containing nonwoven fabric filter UF-APN was used, in Comparative Example 5, the activated carbon-containing nonwoven fabric filter UF-APM was used, and in Comparative Example 6, the activated carbon-containing urethane filter UF-PU3 was used as a deodorizing composition without being subjected to the dropping of the supporting liquid and the drying operation.

[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 deodorizing composition according to the present disclosure has the effect of improving the aldehyde capture performance even when activated carbon is fixed to a filter.

[0087]

[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 added dropwise to 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 aminooxyalkyl group-containing polysiloxane supported relative to the activated carbon and the activated carbon content in the filter were each calculated using the following formulas.

[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] / Mass of the filter [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 (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) carrying 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the acetaldehyde concentration of the eluate was quantified using a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation). Furthermore, the acetaldehyde capture rate was calculated using 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, deodorizing 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 of each composition 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 scavenging performance even when it contains an acid, a base, and a surfactant.

[0095]

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

[0097] <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 4 hours, the gas in the Tedlar bag was adsorbed onto a cartridge (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) carrying 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the acetaldehyde concentration of the eluate was quantified using a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation). Furthermore, the acetaldehyde capture rate was calculated using the following formula.

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

[0099] Furthermore, the deodorizing 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 an acetaldehyde capture test was carried out in the same manner.

[0100] Example 25 In Example 25, a deodorizing composition was prepared in the same manner 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 deodorizing 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]

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

[0104]

[0105] As is clear from Table 5, the deodorizing 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 deodorizing compositions carrying a conventionally known aldehyde trapping agent.

[0106] Example 26 <Preparation of Deodorizing Filter> 16 g of water was added to 1 g of the supporting solution to obtain a 17-fold diluted solution. Two activated carbon-containing nonwoven fabric filters (UES, UF-APM) cut into 5 cm squares were prepared, each immersed in the aforementioned diluted solution, and then passed through a press (Imoto Manufacturing, IMC-6600). Furthermore, using a hot air dryer (Advantec, DRJ433DA), one filter was dried at 60°C for 30 minutes and the other filter was dried at 130°C for 1 hour, thereby obtaining a total of two deodorizing filters with different heating and drying conditions. Furthermore, the amount of deodorizer supported on the activated carbon and the activated carbon content in the filter were calculated using 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]) × 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 ] × 100 <Acetaldehyde Capture Test> Two of the above 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 (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) carrying 2,4-dinitrophenylhydrazine (DNPH). The cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the acetaldehyde concentration of the eluate was quantified using a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation). Furthermore, the acetaldehyde capture rate was calculated using the following formula:

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

[0109] Example 27 In Example 27, a deodorizing 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] In Comparative Example 8, two activated carbon-containing nonwoven fabric filters (UF-APM manufactured by UES) cut into 5 cm squares were prepared, and one was dried at 60° C. for 30 minutes and the other at 130° C. for 1 hour. 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 supporting 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 supporting 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 and 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 scavenger.

[0115]

[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 activated carbon-containing nonwoven fabric filters (UF-APM manufactured by UES) cut into 6 cm squares were prepared and immersed in the aforementioned diluted solution, and then passed through a press (IMC-6600 manufactured by Imoto Machinery Works, Ltd.) to be pressed. Furthermore, three deodorizing filters supporting an 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 deodorizer supported on the activated carbon was calculated using 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 was placed in a stainless steel pipe (cross-sectional area of ​​the flow path: 13 cm ２) flange, 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 inside the sealed container was reduced in pressure by the power of the suction pump, causing the gas inside 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] A 100 L Tedlar bag was charged with 100 L of nitrogen gas with an acetaldehyde concentration of 4 ppm, and the flow rate of the suction pump was set to 0.5 L / min (0.007 m / sec), capturing 3 L of aldehyde gas. The captured gas was adsorbed onto a cartridge (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) loaded with 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile, and the DNPH-aldehyde condensate was eluted. Subsequently, the acetaldehyde concentration of the eluate was quantified using a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation). Furthermore, the acetaldehyde capture rate was calculated using 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 LV-40BW manufactured by Shibata Scientific Instruments, and the flow rate of one of the remaining deodorant compositions 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 collected in the same manner 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 supporting 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 and 29 and Comparative Examples 12 and 13 are shown in Table 7. As is clear from Table 7, the deodorizing filter of the present invention has the 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 conventionally known aldehyde scavengers.

[0126]

[0127] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

[0128] The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2023-171201 filed on October 2, 2023 are hereby incorporated by reference as the disclosure of the specification of the present invention.

[0129] 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): [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 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. The deodorant composition according to claim 1, wherein n is 0 in the aminooxyalkyl group-containing polysiloxane represented by the general formula (1).

4. 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. 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, which comprises contacting an aldehyde-containing gas with the deodorant composition according to any one of claims 1 to 4.

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

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