Deodorizing composition and deodorizing structure

Abstract

The present invention provides a deodorant composition which exhibits more excellent aldehyde capturing effect than conventional deodorant compositions even after water washing or laundering.　The present invention uses a deodorant composition which is characterized by containing a binder resin and a carrier that is loaded with an aminooxy alkyl group by means of a chemical bond.

Description

[Technical Field]

[0001] This invention relates to deodorizing compositions and deodorizing structures. [Background technology]

[0002] Aldehydes such as acetaldehyde and formaldehyde are typical odor-causing substances in living environments. Because their odor threshold is extremely low, even low concentrations can cause unpleasant odors. These aldehydes are emitted from synthetic resins, plywood, and cigarette smoke indoors and in automobiles, and are known to cause sick building syndrome and sick car syndrome. Furthermore, these aldehydes are suspected of being carcinogenic, and daily exposure to them poses a health risk. Therefore, the Ministry of Health, Labour and Welfare has set indoor concentration guidelines of 0.03 ppm for acetaldehyde and 0.08 ppm for formaldehyde. Consequently, there is a need for means to remove aldehydes quickly and sustainably.

[0003] Lower aldehydes such as acetaldehyde and formaldehyde have low boiling points, resulting in low capture efficiency with inorganic porous materials such as silica gel and activated carbon, which are commonly used as deodorizers. Therefore, a method for capturing aldehydes by chemically reacting them with an aldehyde scavenger consisting of a hydrazine derivative, amine, amino acid, or urea derivative has been disclosed (see, for example, Patent Documents 1 to 3). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 4-358536 [Patent Document 2] Japanese Patent Application Publication No. 11-4879 [Patent Document 3] Japanese Patent Publication No. 2018-108360 [Overview of the project] [Problems that the invention aims to solve]

[0005] The methods described in Patent Documents 1 to 3 above have problems such as insufficient capture efficiency and insufficient water resistance, which causes the capture agent applied to substrates such as resins and fibers to dissolve during washing or laundering, resulting in a decrease in performance.

[0006] In view of the background of the prior art, the present invention aims to provide a deodorizing composition that exhibits a superior aldehyde scavenging effect compared to the prior art, even after washing or washing with water. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the inventors of the present invention discovered that a specific deodorizing composition has excellent water resistance, and thus completed the present invention.

[0008] In other words, the present invention includes the following embodiments. [1] A deodorizing composition characterized by comprising a carrier on which aminooxyalkyl groups are supported by chemical bonding and a binder resin. [2] The deodorizing composition according to [1], wherein the carrier on which aminooxyalkyl groups are supported by chemical bonds has one of the structures represented by the following general formula (2).

[0009] [ka]

[0010] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m' represents an integer from 0 to 2. n represents an integer from 1 to 12.) [3] The deodorizing composition according to [2] above, wherein R is a methyl group and X is a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group. [4] The deodorizing composition according to [2] above, wherein n is 3 or 11. [5] The deodorant composition according to [1] or [2], wherein the carrier having an aminooxyalkyl group supported by a chemical bond is a reaction product of a compound represented by the following general formula (1) and an inorganic carrier or a polymer carrier having a hydroxyl group on the surface.

[0011] [Chemical formula]

[0012] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m represents an integer of 0 to 2, and n represents an integer of 1 to 12.) [6] The deodorant composition according to [5], wherein R is a methyl group and X is a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group. [7] The deodorant composition according to [5], wherein n is 3 or 11. [8] The deodorant composition according to any one of [5] to [7], wherein the inorganic carrier is silica gel, alumina, zeolite, magnesia, titania, zirconia, ceria, diatomaceous earth, activated carbon, cellulose, or hydroxyapatite. [9] The deodorant composition according to any one of [5] to [7], wherein the inorganic carrier is silica gel.

[10] The deodorant composition according to any one of [1] to [9], wherein the binder resin is an acrylate resin, a silicone resin, or a urethane resin.

[11] A method for removing aldehyde, comprising exposing the deodorant composition according to any one of [1] to

[10] to a space containing aldehyde and bringing the aldehyde into contact with the deodorant composition. [

[12] ] A deodorant structure having a substrate on which the deodorant composition according to any one of [1] to

[10] is attached.

[13] The deodorizing structure according to

[12] , wherein the base material is a fiber, sheet, wallpaper, sponge, beads, wood, plywood, or gypsum board.

[14] A method for removing aldehydes, characterized by exposing the deodorizing structure described in

[12] or

[13] above to an aldehyde-containing gas and bringing the aldehyde into contact with the deodorizing composition. [Effects of the Invention]

[0013] The present invention provides an aldehyde scavenger that exhibits excellent aldehyde scavenging effect even after washing or rinsing, and has superior water resistance compared to conventional agents. [Modes for carrying out the invention]

[0014] The present invention will be described in detail below.

[0015] The deodorizing composition of the present invention is characterized by comprising a carrier on which aminooxyalkyl groups are chemically bonded and a binder resin.

[0016] The carrier on which the aforementioned aminooxyalkyl group is supported by chemical bonding is not particularly limited, but for example, the following general formula (2)

[0017] [ka]

[0018] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m' represents an integer from 0 to 2. n represents an integer from 1 to 12.) A carrier having any of the structures shown can be given.

[0019] The alkyl group having 1 to 4 carbon atoms represented by R is not particularly limited, but examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-methylpropyl group, 1-methylpropyl group, tert-butyl group, etc.

[0020] For R, a methyl group is preferred because the silane coupling reaction described later is efficient.

[0021] The alkoxy group having 1 to 4 carbon atoms represented by X above is not particularly limited, but examples include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, 2-methylpropyloxy group, 1-methylpropyloxy group, tert-butoxy group, etc.

[0022] For X, a methoxy group, ethoxy group, propoxy group, or isopropoxy group is preferred, more preferably a methoxy group or ethoxy group, and more preferably a methoxy group, in that the silane coupling reaction described later is efficient.

[0023] The aforementioned m' represents an integer between 0 and 2, but it is preferably 0 or 1 in that the silane coupling reaction described later is efficient.

[0024] The aforementioned n represents an integer from 1 to 12, but an integer from 3 to 12 is preferred, and 3 or 11 is more preferred, in terms of superior aldehyde scavenging effect.

[0025] The carrier on which the aforementioned aminooxyalkyl group is supported by chemical bonding is not particularly limited, but for example, the following general formula (1)

[0026] [ka]

[0027] (In the formula, R represents an alkyl group having 1 to 4 carbon atoms. X represents an alkoxy group having 1 to 4 carbon atoms. m represents an integer from 0 to 2, and n represents an integer from 1 to 12.) Preferably, the reaction product is obtained by mixing a compound represented by (hereinafter also referred to as "silane coupling agent") with a support having hydroxyl groups on its surface (hereinafter, the reaction is also referred to as "silane coupling reaction").

[0028] In other words, a carrier on which the aforementioned aminooxyalkyl group is supported by chemical bonding can be produced by reacting the above-mentioned silane coupling agent with a carrier having hydroxyl groups on its surface.

[0029] In the silane coupling agent described above, the definitions and preferred ranges of R, X, and n are the same as the definitions and preferred ranges of R, X, and n in the general formula (2) described above.

[0030] In the silane coupling agent described above, m represents an integer between 0 and 2. For m, it is preferable that it be 0 or 1, as this ensures an efficient silane coupling reaction.

[0031] The silane coupling agent mentioned above may be purchased commercially, but it can also be synthesized according to the methods described in Organic Preparations and Procedures International, vol.26, 1994, 111-113, Japanese Patent Publication No. Hei 7-233132, and Tetrahedron Letters, Vol.46(14), 2005, 7973-7975.

[0032] The deodorizing composition of the present invention is, as described above, an aminooxyalkyl group (-(CH2) in general formulas (1) and (2)) n The present invention is characterized by having a group represented by -ONH2, but some or all of the aminooxyalkyl group may be a chemically acceptable salt with an inorganic acid or an organic acid.

[0033] The type of salt is not particularly limited, but examples include inorganic salts such as hydrochloride, hydrobromide, perchlorate, silicate, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate, or phosphate, or organic salts such as acetate, citrate, fumarate, maleate, trifluoromethanesulfonate, trifluoroacetate, benzoate, or p-toluenesulfonate. Of the salts, inorganic salts are preferred because they are inexpensive, and hydrochloride salts are even more preferred.

[0034] The amount of aminooxyalkyl groups supported on the carrier on which the above-mentioned aminooxyalkyl groups are chemically bonded can be arbitrarily adjusted depending on the purpose and is not particularly limited, but a range of 0.01 to 10 mmol / g is preferred based on the unit weight of the carrier on which the aminooxyalkyl groups are chemically bonded.

[0035] The above-mentioned carriers are not particularly limited, but examples include polymer carriers and inorganic carriers.

[0036] The aforementioned polymer carriers are not particularly limited, but examples include styrene polymers (e.g., polystyrene or cross-linked polystyrene), polyolefins (e.g., polyethylene or polypropylene), poly(halogenated olefins) (e.g., polyvinyl chloride or polytetrafluoroethylene), nitrile polymers (e.g., polyacrylonitrile), (meth)acrylic polymers (e.g., polymethyl methacrylate or ethyl polyacrylate), and high molecular weight polysaccharides (e.g., cellulose, agarose, or dextran).

[0037] The inorganic support mentioned above is not particularly limited, but examples include silica gel, alumina, zeolite, magnesia, titania, zirconia, ceria, diatomaceous earth, activated carbon, cellulose, hydroxyapatite, and the like.

[0038] The support is preferably an inorganic support in that the above-mentioned silane coupling reaction is efficient, more preferably silica gel, alumina, zeolite, magnesia, titania, zirconia, ceria, diatomaceous earth, activated carbon, cellulose, or hydroxyapatite, and even more preferably silica gel.

[0039] Furthermore, it is preferable that the carrier in question has hydroxyl groups on its surface.

[0040] The shape of the carrier is not particularly limited, but examples include spherical, granular, fibrous, granular, monolithic column, hollow fiber, or membrane. Regarding the shape, spherical, membrane, granular, granular, or fibrous shapes are preferred in terms of their excellent aldehyde scavenging effect, and spherical, granular, or granular shapes are more preferred.

[0041] The particle size of the spherical, granular, or granular carrier is preferably in the range of an average particle size of 0.1 μm to 10 mm, and more preferably an average particle size of 1 μm to 100 μm for good dispersibility in liquid.

[0042] The aforementioned carrier may be porous or non-porous, but it is preferable that it be porous in that it has excellent aldehyde scavenging effect.

[0043] When the carrier is a porous carrier, the average pore size of the porous carrier is preferably 1 nm to 1 μm, and more preferably 1 nm to 300 nm in terms of excellent aldehyde scavenging effect.

[0044] The binder resin included in the deodorizing composition of the present invention is not particularly limited, but examples include acrylic ester resin, silicone resin, urethane resin, polyester resin, melamine resin, polypropylene resin, and fluororesin.

[0045] For the binder resin, acrylic ester resin, silicone resin, or urethane resin is preferred in terms of its excellent adhesion to the carrier on which the aminooxyalkyl group is chemically bonded and its water resistance.

[0046] In the above-mentioned deodorizing composition, the weight ratio of the carrier on which the above-mentioned aminooxyalkyl group is chemically supported to the binder resin can be arbitrarily adjusted according to the purpose and is not particularly limited, but a range of carrier on which the aminooxyalkyl group is chemically supported (weight): binder resin (weight) = 1:1000 to 100:1 is preferred, a range of carrier on which the aminooxyalkyl group is chemically supported (weight): binder resin (weight) = 1:100 to 100:1 is more preferred, and a range of carrier on which the aminooxyalkyl group is chemically supported (weight): binder resin (weight) = 1:1.2 to 10:1 is even more preferred.

[0047] The deodorizing composition of the present invention is characterized by comprising a carrier on which aminooxyalkyl groups are chemically bonded and a binder resin. However, the deodorizing composition is not particularly limited, and can be produced by mixing the carrier on which aminooxyalkyl groups are chemically bonded and the binder resin. Alternatively, it can be produced by drying the deodorizing suspension composition described later.

[0048] The deodorizing composition of the present invention may further contain a solvent.

[0049] The solvent is not particularly limited, but examples include water, ethanol, methanol, propanol, and acetonitrile. Among these, water is preferred because it has excellent aldehyde scavenging effect.

[0050] When the deodorizing composition of the present invention contains the aforementioned solvent (the mixture containing the solvent is included in the deodorizing composition of the present invention), if the amount of the solvent becomes relatively large, it will form a suspension. This suspension will be referred to below as the deodorizing suspension composition.

[0051] In the above-mentioned deodorizing suspension composition, the weight ratio of the total amount of the carrier on which the aminooxyalkyl group is chemically supported and the binder resin to the solvent can be arbitrarily adjusted depending on the purpose and is not particularly limited, but the range of total amount (weight):solvent (weight) = 1:1000 to 1:2 is preferred, the range of total amount (weight):solvent (weight) = 1:100 to 1:4 is more preferred, and the range of total amount (weight):solvent (weight) = 1:50 to 1:4 is even more preferred.

[0052] The deodorizing suspension composition is not particularly limited, but for example, it can be produced by mixing and stirring a carrier on which the aminooxyalkyl group is supported by chemical bonding, the binder resin, and the solvent.

[0053] The methods of using the aforementioned deodorizing composition or deodorizing suspension composition are not particularly limited, but examples include directly contacting or spraying the deodorizing composition or deodorizing suspension composition with a source of odor (including aldehydes), or exposing or spraying it into a gas containing odor-causing substances (including aldehydes) that cause malodors.

[0054] The aforementioned sources of odor are not limited to, but examples include organic solvent-based adhesives, new building materials, and plywood.

[0055] By directly contacting or spraying the aforementioned deodorizing composition or deodorizing suspension composition onto the odor source, the odor-causing substances are captured by the deodorizing composition or deodorizing suspension composition. This reduces the amount of odor emitted from the odor source.

[0056] Furthermore, by exposing or spraying the aforementioned deodorizing composition or deodorizing suspension composition into a gas containing odor-causing substances (including aldehydes) that cause malodors, the odor-causing substances are captured by the deodorizing composition or deodorizing suspension composition. This reduces the amount of odor in the gas.

[0057] The aforementioned odor-causing substances are not limited to, but examples include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, isovaleraldehyde, hexanal, hexenal, nonenal, methyl isobutyl ketone, diacetyl, ethyl acetate, acetic acid, propionic acid, n-butyric acid, n-valeric acid, isovaleric acid, methyl mercaptan, or ethyl mercaptan.

[0058] Other methods of using the aforementioned deodorizing composition or deodorizing suspension composition are not limited to those mentioned above, but include, for example, using the deodorizing composition or deodorizing suspension composition in a state where it is attached to a substrate, and using the substrate on which the deodorizing composition or deodorizing suspension composition is attached as a deodorizing structure.

[0059] The aforementioned deodorizing structure can be manufactured by applying or spraying the aforementioned deodorizing composition or deodorizing suspension composition onto a substrate.

[0060] The aforementioned deodorizing structure can reduce the odor of the gas by being exposed to a gas containing odor-causing substances (including aldehydes) that cause malodors, thereby capturing the odor-causing substances in the gas.

[0061] The aforementioned base material is not particularly limited, but examples include fibers, sheets, wallpaper, sponge, beads, wood, plywood, or gypsum board.

[0062] The materials for the aforementioned fibers, sheets, wallpaper, or sponges are not particularly limited, but include, for example, polyester, polyamide, polyacrylonitrile, polypropylene, polyethylene, polyvinyl chloride, fluororesins, aramid resins, sulfone resins, rayon, acetate, cotton, wool, silk, hemp, glass, carbon, ceramics, silicone resins, polyimide resins, natural rubber, polyurethane, and the like.

[0063] The aforementioned deodorizing structures are not particularly limited, but examples include clothing, curtains, carpets, wall coverings, automotive interior materials, or furniture.

[0064] The amount of the deodorizing composition immobilized on the substrate can be arbitrarily adjusted according to the purpose and is not particularly limited, but based on the unit area of ​​the substrate, the amount of the deodorizing composition is 0.1 to 200 g / m². 2 Preferably, the range is 0.5 to 75 g / m 2 It is more preferable that it be within that range.

[0065] The amount of support immobilized on the substrate by chemical bonding of aminooxyalkyl groups can be arbitrarily adjusted according to the purpose and is not particularly limited, but based on the unit area of ​​the substrate, the amount of support immobilized by chemical bonding of the aminooxyalkyl groups is 0.09 to 180 g / m². 2 Preferably, the range is 0.45 to 68 g / m 2 It is more preferable that it be within that range. [Examples]

[0066] The present invention 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 in any way by these examples. Unless otherwise specified, the reagents used were commercially available products.

[0067] The analytical instruments and evaluation methods used in this embodiment are listed below.

[0068] <Acetaldehyde Capture Test> After sealing the deodorizing structure described later in a 5L Tedlar bag, 3L of nitrogen gas with an acetaldehyde concentration of approximately 14 ppm was added. After standing at room temperature for 2 hours, the entire amount of gas in the Tedlar bag was adsorbed onto a cartridge (Presep-C DNPH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) supporting 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the DNPH-aldehyde condensate was quantified using a liquid chromatograph (LC-2030C Plus, manufactured by Shimadzu Corporation) and the residual acetaldehyde concentration inside the Tedlar bag was calculated. Furthermore, the aldehyde capture rate [%] was calculated using the following formula.

[0069] Acetaldehyde capture rate [%] = [(Initial acetaldehyde concentration - Residual acetaldehyde concentration) ÷ Initial acetaldehyde concentration] × 100 Synthesis Example 1 A mixture of 19.94 g of silica gel with an average particle size of 4 μm (Tosoh Silica, NIPGEL BY-400) and 173.4 g of toluene was mixed with a mixture of 8.08 g of a silane coupling agent represented by chemical formula (1a) and 43.35 g of toluene, and the mixture was stirred at 25°C for 120 hours under a nitrogen atmosphere. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain a support on which aminooxyalkyl groups were chemically bonded (hereinafter referred to as "aminooxy group-supported support"). Elemental analysis of the obtained aminooxy group-supported support revealed that the aminooxyalkyl group was present at a concentration of 1.4 mmol / g relative to the weight of the aminooxy group-supported support.

[0070] [ka]

[0071] The infrared absorption spectra (hereinafter referred to as IR spectra) of untreated silica gel (NIPGEL BY-400, manufactured by Tosoh Silica) and the aforementioned aminooxy group supported carrier were measured. As a result, the untreated silica gel showed an infrared absorption spectrum of 970 cm⁻¹. -1The silanol Si-O bending vibration peak that was present in the vicinity disappeared in the aminooxy group supported carrier. These results indicate that the hydroxyl groups on the surface of silica gel are chemically modified by the silane coupling agent represented by chemical formula (1a).

[0072] Synthesis Example 2 A mixture of 16.88 g of silica gel (Tosoh Silica, NIPGEL BY-001) with an average particle size of 14 μm, 44.87 g of toluene, and 16.88 g of distilled water was mixed with a mixture of 5.42 g of the silane coupling agent represented by the above chemical formula (1a) and 22.66 g of toluene, under a nitrogen stream. The mixture was stirred under heating and reflux for 4 hours. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain an aminooxy group-supported carrier. Elemental analysis of the obtained aminooxy group-supported carrier revealed that it contained 1.5 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy group-supported carrier.

[0073] The IR spectra of untreated silica gel (manufactured by Tosoh Silica, NIPGEL BY-001) and the aforementioned aminooxy group supported carrier were measured. As a result, the untreated silica gel measured 970 cm⁻¹. -1 The silanol Si-O bending vibration peak that was present in the vicinity disappeared in the aminooxy group supported carrier. These results indicate that the hydroxyl groups on the surface of silica gel are chemically modified by the silane coupling agent represented by chemical formula (1a).

[0074] Synthesis Example 3 A mixture of 16.88 g of silica gel (manufactured by Tosoh Silica, NIPSIL NS-T) with an average particle size of 21 μm, 45.00 g of toluene, and 16.88 g of distilled water was prepared. Under a nitrogen stream, a mixture of 5.40 g of the silane coupling agent represented by the above chemical formula (1a) and 22.72 g of toluene was added dropwise and stirred under heating and reflux for 4 hours. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain an aminooxy group-supported carrier. Elemental analysis of the obtained aminooxy group-supported carrier revealed that it contained 1.4 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy group-supported carrier.

[0075] The IR spectra of untreated silica gel (manufactured by Tosoh Silica, NIPSIL NS-T) and the aforementioned aminooxy group supported carrier were measured. As a result, the silica gel measured 970 cm⁻¹. -1 The silanol Si-O bending vibration peak that was present in the vicinity disappeared in the aminooxy group supported carrier. These results indicate that the hydroxyl groups on the surface of silica gel are chemically modified by the silane coupling agent represented by chemical formula (1a).

[0076] Synthesis Example 4 3.05 g of silica gel with an average particle size of 4 μm (Tosoh Silica, NIPGEL BY-400), 12.22 g of toluene, 0.46 g of distilled water, and 0.90 g of a silane coupling agent represented by the following chemical formula (1b) were mixed and stirred for 4 hours under a nitrogen stream and heated reflux. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain an aminooxy group-supported carrier. Elemental analysis of the obtained aminooxy group-supported carrier revealed that it contained 1.1 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy group-supported carrier.

[0077] [ka]

[0078] The untreated product of silica gel (manufactured by Tosoh Silica, NIPGEL BY-400) and the IR spectrum of the above aminooxy group-bearing carrier were measured. As a result, in the above silica gel, the silanol Si-O bending vibration peak present around 970 cm -1 had disappeared in the above aminooxy group-bearing carrier. From these results, it was found that the surface hydroxyl groups of silica gel were chemically modified by the silane coupling agent represented by the above chemical formula (1b).

[0079] Synthesis Example 5 2.44 g of silica gel (manufactured by Tosoh Silica, NIPGEL BY-400) with an average particle size of 4 μm, 9.78 g of toluene, 0.37 g of distilled water, and 0.95 g of a silane coupling agent represented by the following chemical formula (1c) were mixed, and then stirred under heating and reflux for 4 hours under a nitrogen stream. The obtained reaction solution was filtered, and the residue was dried at 120 °C for 4 hours to obtain an aminooxy group-bearing carrier. When the obtained aminooxy group-bearing carrier was subjected to elemental analysis, it was found that the aminooxyalkyl group was contained at 0.9 mmol / g based on the weight of the aminooxy group-bearing carrier.

[0080]

Chemical formula

[0081] The untreated product of silica gel (manufactured by Tosoh Silica, NIPGEL BY-400) and the IR spectrum of the above aminooxy group-bearing carrier were measured. As a result, in the above silica gel, the silanol Si-O bending vibration peak present around 970 cm -1 had disappeared in the above aminooxy group-bearing carrier. From these results, it was found that the surface hydroxyl groups of silica gel were chemically modified by the silane coupling agent represented by the above chemical formula (1c).

[0082] Synthesis Example 6 1.83 g of silica gel with an average particle size of 4 μm (Tosoh Silica, NIPGEL BY-400), 7.32 g of toluene, 0.27 g of distilled water, and 0.93 g of a silane coupling agent represented by the following chemical formula (1d) were mixed and stirred for 4 hours under a nitrogen stream and heated reflux. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain an aminooxy group-supported carrier. Elemental analysis of the obtained aminooxy group-supported carrier revealed that it contained 0.8 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy group-supported carrier.

[0083] [ka]

[0084] The IR spectra of untreated silica gel (Tosoh Silica, NIPGEL BY-400) and the aforementioned aminooxy group supported carrier were measured. As a result, the silica gel measured 970 cm⁻¹. -1 The silanol Si-O bending vibration peak that was present in the vicinity disappeared in the aminooxy group supported carrier. These results indicate that the hydroxyl groups on the surface of silica gel are chemically modified by the silane coupling agent represented by the chemical formula (1d) above.

[0085] Synthesis Example 7 3.05 g of powdered coconut shell activated carbon (manufactured by Osaka Gas Chemical, Shirasagi M), 12.30 g of toluene, 0.45 g of distilled water, and 0.97 g of the silane coupling agent represented by the above chemical formula (1a) were mixed and stirred for 4 hours under a nitrogen stream and heated reflux. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain an aminooxy group supported carrier. Elemental analysis of the obtained aminooxy group supported carrier revealed that it contained 1.4 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy group supported carrier.

[0086] Synthesis Example 8 3.05 g of powdered woody activated carbon (Carboraffin, manufactured by Osaka Gas Chemical Co., Ltd.), 12.24 g of toluene, 0.46 g of distilled water, and 0.98 g of the silane coupling agent represented by the above chemical formula (1a) were mixed and stirred for 4 hours under a nitrogen stream and heated reflux. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain an aminooxy group supported support. Elemental analysis of the obtained aminooxy group supported support revealed that it contained 1.6 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy group supported support.

[0087] Example 1 A deodorizing composition (deodorizing suspension composition) was obtained by mixing 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 1, 0.24 g of acrylic acid ester binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K), and 9.56 g of distilled water in a polyethylene container.

[0088] The obtained deodorizing composition (deodorizing suspension composition) was applied at a rate of 750 μL (0.75 g) to a 10 cm x 10 cm 100% polyester fabric fiber, and dried at 150°C for 3 minutes using a hot air dryer (Advantec Co., Ltd., DRJ433DA) to obtain a deodorizing structure in which the deodorizing composition was immobilized.

[0089] Next, the obtained deodorizing structure was subjected to washing by repeating the washing durability test method (JIS L 0217 103 method) five times.

[0090] Next, an acetaldehyde capture test was conducted using the deodorizing structure before and after washing.

[0091] Example 2 Except for using 0.24 g of silicone-based binder resin (Vintex S-200L, manufactured by Yamato Chemical Industry Co., Ltd.) instead of 0.24 g of acrylic acid ester-based binder resin (Ficoat 70K, manufactured by Yamato Chemical Industry Co., Ltd.) as in Example 1, a deodorizing composition (deodorizing suspension composition) and a deodorizing structure were manufactured and evaluated in the same manner as in Example 1.

[0092] Example 3 The procedure was carried out in the same manner as in Example 1, except that 0.24 g of urethane-based binder resin (manufactured by Yamato Chemical Industry Co., Ltd., U-30NP) was used instead of 0.24 g of acrylic acid ester-based binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K) as in Example 1.

[0093] Example 4 Except for using 10cm x 10cm 100% cotton fabric fibers instead of the 10cm x 10cm 100% polyester fabric fibers used in Example 1, a deodorizing composition (deodorizing suspension composition) and a deodorizing structure were manufactured and evaluated in the same manner as in Example 1.

[0094] Example 5 Except for changing the application amount of the deodorizing composition (deodorizing suspension composition) from 750 μL (0.75 g) to 250 μL (0.25 g) in Example 1, the deodorizing composition (deodorizing suspension composition) and the deodorizing structure were manufactured and evaluated in the same manner as in Example 1.

[0095] Example 6 Except for changing the amount of acrylic acid ester binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K) from 0.24 g to 0.08 g and the amount of distilled water from 9.56 g to 9.72 g, the deodorizing composition (deodorizing suspension composition) and deodorizing structure were manufactured and evaluated in the same manner as in Example 1.

[0096] Example 7 Except for changing the amount of acrylic acid ester binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K) from 0.24 g to 0.02 g and the amount of distilled water from 9.56 g to 9.78 g, the deodorizing composition (deodorizing suspension composition) and deodorizing structure were manufactured and evaluated in the same manner as in Example 1.

[0097] Example 8 In Example 1, the procedure was carried out in the same manner as in Example 1, except that 0.20 g of the aminooxy group support obtained in Synthesis Example 1 was replaced with 0.20 g of the aminooxy group support obtained in Synthesis Example 2. A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were then produced and evaluated.

[0098] Example 9 In Example 1, the procedure was carried out in the same manner as in Example 1, except that 0.20 g of the aminooxy group support obtained in Synthesis Example 1 was replaced with 0.20 g of the aminooxy group support obtained in Synthesis Example 3. A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were then produced and evaluated.

[0099] Example 10 In Example 1, the procedure was carried out in the same manner as in Example 1, except that 0.20 g of the aminooxy group support obtained in Synthesis Example 1 was replaced with 0.20 g of the aminooxy group support obtained in Synthesis Example 4. A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were then produced and evaluated.

[0100] Example 11 Except for replacing 0.20 g of the aminooxy group support obtained in Synthesis Example 1 with 0.20 g of the aminooxy group support obtained in Synthesis Example 5, the procedure was carried out in the same manner as in Example 1 to produce and evaluate a deodorizing composition (deodorizing suspension composition) and a deodorizing structure.

[0101] Example 12 In Example 1, the procedure was carried out in the same manner as in Example 1, except that 0.20 g of the aminooxy group support obtained in Synthesis Example 1 was replaced with 0.20 g of the aminooxy group support obtained in Synthesis Example 6. A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were then produced and evaluated.

[0102] Example 13 Except for replacing 0.20 g of the aminooxy group support obtained in Synthesis Example 1 with 0.20 g of the aminooxy group support obtained in Synthesis Example 7 in Example 1, the procedure was carried out in the same manner as in Example 1 to produce and evaluate a deodorizing composition (deodorizing suspension composition) and a deodorizing structure.

[0103] Example 14 In Example 1, the procedure was carried out in the same manner as in Example 1, except that 0.20 g of the aminooxy group support obtained in Synthesis Example 1 was replaced with 0.20 g of the aminooxy group support obtained in Synthesis Example 8. A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were then produced and evaluated.

[0104] Comparative Example 1 Except for not adding 0.24 g of acrylic acid ester binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K) as in Example 4, and changing the amount of distilled water from 9.56 g to 9.80 g, the deodorizing composition (deodorizing suspension composition) and deodorizing structure were manufactured and evaluated in the same manner as in Example 4.

[0105] Comparative Example 2 Except for not adding 0.20 g of aminooxy group-supported carrier in Example 4 and changing the amount of distilled water from 9.56 g to 9.76 g, the deodorizing composition (deodorizing suspension composition) and deodorizing structure were manufactured and evaluated in the same manner as in Example 4.

[0106] Comparative Example 3 In Example 4, instead of using 10.0 g of a deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of an aminooxy group-supported carrier, 0.24 g of an acrylic acid ester-based binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K), and 9.56 g of distilled water, 10.0 g of a 3% by weight aqueous solution of aminooxyacetic acid was used. Otherwise, the deodorizing structure was manufactured and evaluated in the same manner as in Example 4.

[0107] Comparative Example 4 In Example 4, instead of using 10.0 g of a deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of an aminooxy group-supported carrier, 0.24 g of an acrylic acid ester-based binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K), and 9.56 g of distilled water, 10.0 g of a 3% by weight aqueous solution of adipic acid dihydrazide was used. Otherwise, the deodorizing structure was manufactured and evaluated in the same manner as in Example 4.

[0108] Comparative Example 5 Except for not adding 0.24 g of acrylic acid ester binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K) as in Example 1, and changing the amount of distilled water from 9.56 g to 9.80 g, a deodorizing composition (deodorizing suspension composition) and a deodorizing structure were manufactured and evaluated in the same manner as in Example 1.

[0109] Comparative Example 6 In Example 1, instead of using 10.0 g of a deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of an aminooxy group-supported carrier, 0.24 g of an acrylic acid ester binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K), and 9.56 g of distilled water, a deodorizing structure was manufactured and evaluated in the same manner as in Example 1, except that 10.0 g of a deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of a commercially available inorganic aldehyde scavenger (manufactured by Toagosei, Kesmon NS750), 0.24 g of an acrylic acid ester binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K), and 9.56 g of distilled water was used.

[0110] Comparative Example 7 In Example 1, instead of using 10.0 g of a deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of an aminooxy group-supported carrier, 0.24 g of an acrylic acid ester binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K), and 9.56 g of distilled water, a deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of a commercially available inorganic aldehyde scavenger (manufactured by Toagosei, Kesmon NS750), 0.08 g of an acrylic acid ester binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K), and 9.72 g of distilled water, a deodorizing structure was manufactured and evaluated in the same manner as in Comparative Example 6.

[0111] Comparative Example 8 In Example 1, instead of using 10.0 g of a deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of aminooxy group-supported carrier, 0.24 g of acrylic acid ester binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K), and 9.56 g of distilled water, a deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of unmodified silica gel (manufactured by Tosoh Silica, NIPSIL BY-400), 0.24 g of acrylic acid ester binder resin (manufactured by Yamato Chemical Industry Co., Ltd., Ficoat 70K), and 9.56 g of distilled water, a deodorizing structure was manufactured and evaluated in the same manner as in Example 1.

[0112] The results for Examples 1 to 14 are shown in Table 1, and the results for Comparative Examples 1 to 8 are shown in Table 2. As is clear from Tables 1 and 2, the deodorizing compositions of the present invention showed superior water resistance compared to existing deodorizing compositions.

[0113] [Table 1]

[0114] [Table 2]

[0115] Furthermore, the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2021-054339, filed on March 26, 2021, are incorporated herein by reference as disclosure of the specification of the present invention.

Claims

1. A deodorizing structure having a substrate on which a deodorizing composition is attached, characterized by containing a carrier on which aminooxyalkyl groups are supported by chemical bonding via a silane coupling reaction and a binder resin.

2. The deodorizing structure according to claim 1, wherein the binder resin is an acrylic ester resin, a silicone resin, or a urethane resin.

3. The deodorizing structure according to claim 1 or 2, wherein the base material is a fiber, sheet, wallpaper, sponge, beads, wood, plywood, or gypsum board.

4. A method for removing aldehydes, characterized by exposing the deodorizing structure according to any one of claims 1 to 3 to an aldehyde-containing gas and bringing the aldehyde into contact with the deodorizing composition.

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