Deodorant composition and deodorant 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

Deodorizing composition and deodorizing structure

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

[0002] Aldehydes, such as acetaldehyde and formaldehyde, are typical odorants in living environments. Because their odor threshold is extremely low, even low concentrations can cause unpleasant odors. These aldehydes are generated indoors and in automobiles from synthetic resins, plywood, cigarette smoke, and other sources, 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, Labor, and Welfare has set indoor concentration guidelines of 0.03 ppm for acetaldehyde and 0.08 ppm for formaldehyde. Therefore, there is a need for a means to rapidly and sustainably remove aldehydes.

[0003] Lower aldehydes such as acetaldehyde and formaldehyde have low boiling points, and therefore, inorganic porous materials commonly used as deodorizers, such as silica gel and activated carbon, have low trapping efficiency. Therefore, methods for trapping aldehydes by chemically reacting the aldehydes with aldehyde trapping agents such as hydrazine derivatives, amines, amino acids, or urea derivatives have been disclosed (see, for example, Patent Documents 1 to 3).

[0004] JP 4-358536, JP 11-4879, JP 2018-108360

[0005] The methods described in the above Patent Documents 1 to 3 have problems such as not necessarily having sufficient capture efficiency and not having sufficient water resistance, so that the capture agent applied to a substrate such as a resin or fiber is eluted by washing with water 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 capturing effect compared to the prior art, even after washing with water or laundering.

[0007] As a result of extensive research aimed at solving the above problems, the present inventors have found that a specific deodorant composition has excellent water resistance, and have thus completed the present invention.

[0008] That is, the present invention includes the following embodiments: [1] A deodorizing composition comprising a carrier having an aminooxyalkyl group supported thereon by a chemical bond and a binder resin. [2] The deodorizing composition according to the above [1], wherein the carrier having an aminooxyalkyl group supported thereon by a chemical bond has any structure represented by the following general formula (2):

[0009]

[0010] (wherein 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.) [3] The deodorizing composition according to the above item [2], 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 the above item [2], wherein n is 3 or 11. [5] The deodorizing composition according to the above item [1] or [2], wherein the carrier having aminooxyalkyl groups supported thereon by chemical bonding is a reaction product of a compound represented by the following general formula (1) and an inorganic carrier or a polymer carrier having hydroxyl groups on the surface:

[0011]

[0012] (wherein 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 deodorizing composition according to the above item [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 deodorizing composition according to the above item [5], wherein n is 3 or 11. [8] The deodorizing composition according to any one of the above items [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 deodorizing composition according to any one of the above items [5] to [7], wherein the inorganic carrier is silica gel.

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

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

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

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

[10] adhered to its surface.

[13] The deodorizing structure according to

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

[14] A method for removing aldehyde, comprising exposing the deodorizing structure according to

[12] or

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

[0013] The present invention can provide an aldehyde scavenger that exhibits excellent aldehyde scavenging effect even after rinsing or laundering and has better water resistance than conventional agents.

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

[0015] The deodorant composition of the present invention is characterized by comprising a carrier having aminooxyalkyl groups supported thereon by chemical bonding, and a binder resin.

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

[0017]

[0018] (wherein 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).

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

[0020] The R is preferably a methyl group, since the silane coupling reaction described below is efficient.

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

[0022] Regarding X, in terms of the efficiency of the silane coupling reaction described below, a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even more preferable.

[0023] The above m' represents an integer of 0 to 2, but is preferably 0 or 1 in terms of the efficiency of the silane coupling reaction described below.

[0024] The above n represents an integer of 1 to 12, but is preferably an integer of 3 to 12, and more preferably 3 or 11, in terms of excellent aldehyde scavenging effect.

[0025] The carrier on which the aminooxyalkyl group is supported by chemical bonding is not particularly limited, but may be, for example, a carrier having a structure represented by the following general formula (1):

[0026]

[0027] (wherein 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) (hereinafter also referred to as "silane coupling agent") and a carrier having hydroxyl groups on the surface thereof.

[0028] That is, the support having the aminooxyalkyl group supported thereon by chemical bonding can be produced by reacting the above-mentioned silane coupling agent with a support having hydroxyl groups on its surface.

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

[0030] In the silane coupling agent, m represents an integer of 0 to 2. In terms of efficiency of the silane coupling reaction, m is preferably 0 or 1.

[0031] The silane coupling agent may be a commercially available product, or may be synthesized according to the methods described in Organic Preparations and Procedures International, vol. 26, 1994, pp. 111-113, JP-A-7-233132, and Tetrahedron Letters, vol. 46(14), 2005, pp. 7973-7975.

[0032] As described above, the deodorant composition of the present invention is an aminooxyalkyl group (—(CH ２ ) ｎ -ONH ２The aminooxyalkyl groups may be in the form of a chemically acceptable salt with an inorganic acid or an organic acid, either partially or entirely.

[0033] The type of the salt is not particularly limited, and examples thereof include inorganic acid salts such as hydrochloride, hydrobromide, perchlorate, silicate, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate, and phosphate, and organic acid salts such as acetate, citrate, fumarate, maleate, trifluoromethanesulfonate, trifluoroacetate, benzoate, and p-toluenesulfonate. With regard to the salt, inorganic acid salts are preferred in terms of inexpensiveness, and hydrochloride is more preferred.

[0034] The amount of the aminooxyalkyl group supported on the support on which the aminooxyalkyl group is supported by a chemical bond can be adjusted as desired depending on the purpose and is not particularly limited, but is preferably in the range of 0.01 to 10 mmol / g based on the unit weight of the support on which the aminooxyalkyl group is supported by a chemical bond.

[0035] The carrier is not particularly limited, but examples thereof include polymer carriers and inorganic carriers.

[0036] The polymer carrier is not particularly limited, but examples thereof include styrene-based polymers (e.g., polystyrene, cross-linked polystyrene, etc.), polyolefins (e.g., polyethylene, polypropylene, etc.), poly(halogenated olefins) (e.g., polyvinyl chloride, polytetrafluoroethylene, etc.), nitrile-based polymers (e.g., polyacrylonitrile, etc.), (meth)acrylic polymers (e.g., polymethyl methacrylate, polyethyl acrylate, etc.), and high-molecular-weight polysaccharides (e.g., cellulose, agarose, dextran, etc.).

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

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

[0039] The carrier preferably has hydroxyl groups on its surface.

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

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

[0042] The carrier may be porous or non-porous, but is preferably porous in view of its excellent aldehyde capturing 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 capture effect.

[0044] The binder resin contained in the deodorant composition of the present invention is not particularly limited, but examples thereof include acrylic ester resins, silicone resins, urethane resins, polyester resins, melamine resins, polypropylene resins, and fluororesins.

[0045] The binder resin is preferably an acrylic ester resin, a silicone resin, or a urethane resin, because they have excellent water resistance and adhesion to the carrier on which the aminooxyalkyl group is supported by chemical bonding.

[0046] In the deodorant composition, the weight ratio of the carrier carrying the aminooxyalkyl group by chemical bonding to the binder resin can be adjusted as desired depending on the purpose and is not particularly limited, but is preferably in the range of carrier carrying the aminooxyalkyl group by chemical bonding (weight):binder resin (weight) = 1:1000 to 100:1, more preferably carrier carrying the aminooxyalkyl group by chemical bonding (weight):binder resin (weight) = 1:100 to 100:1, and more preferably carrier carrying the aminooxyalkyl group by chemical bonding (weight):binder resin (weight) = 1:1.2 to 10:1.

[0047] The deodorizing composition of the present invention is characterized by comprising a carrier carrying an aminooxyalkyl group by chemical bonding and a binder resin, and although there are no particular limitations on the deodorizing composition, the deodorizing composition can be produced by mixing the carrier carrying the aminooxyalkyl group by chemical bonding with the binder resin. Alternatively, the deodorizing composition can be produced by drying a deodorizing suspension composition described below.

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

[0049] The solvent is not particularly limited, but examples thereof include water, ethanol, methanol, propanol, acetonitrile, etc. Among these, water is preferred because of its excellent aldehyde scavenging effect.

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

[0051] In the deodorant suspension composition, the weight ratio of the total amount of the carrier carrying the aminooxyalkyl group by chemical bonding and the binder resin to the solvent can be adjusted as desired depending on the purpose and is not particularly limited, but is preferably in the range of 1:1000 to 1:2, more preferably 1:100 to 1:4, and even more preferably 1:50 to 1:4.

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

[0053] The method of using the deodorizing composition or deodorizing suspension composition is not particularly limited, but examples thereof include a method of directly contacting the deodorizing composition or deodorizing suspension composition with or spraying it onto an odor (including aldehyde) generating source, or a method of exposing the composition or deodorizing suspension composition to or spraying it into a gas containing odor-causing substances (including aldehyde) that cause bad odors.

[0054] The odor sources are not particularly limited, but examples thereof include organic solvent-based adhesives, new building materials, plywood, and the like.

[0055] By directly contacting or spraying the deodorizing composition or deodorizing suspension composition with the odor source, the odorous substance is captured in the deodorizing composition or deodorizing suspension composition, thereby reducing the amount of odor emitted from the odor source.

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

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

[0058] Other methods of using the deodorizing composition or deodorizing suspension composition include, but are not limited to, a method in which the deodorizing composition or deodorizing suspension composition is used in a state in which it is adhered to a substrate, and a method in which a substrate having the deodorizing composition or deodorizing suspension composition adhered to its surface is used as a deodorizing structure.

[0059] The deodorizing structure can be produced by applying or spraying the deodorizing composition or deodorizing suspension composition to a substrate.

[0060] The deodorizing structure can capture the odor-causing substances in a gas containing the odor-causing substances (including aldehydes) that cause bad odors, thereby reducing the bad odor of the gas.

[0061] The substrate is not particularly limited, but examples thereof include fibers, sheets, wallpaper, sponges, beads, wood, plywood, and gypsum boards.

[0062] The material for the fibers, sheets, wallpaper, or sponges is not particularly limited, but examples thereof include polyester, polyamide, polyacrylonitrile, polypropylene, polyethylene, polyvinyl chloride, fluorine-based resins, aramid resins, sulfone-based resins, rayon, acetate, cotton, wool, silk, hemp, glass, carbon, ceramics, silicone resins, polyimide resins, natural rubber, and polyurethane.

[0063] The deodorizing structure is not particularly limited, but examples thereof include clothing, curtains, carpets, wall coverings, automobile interior materials, and furniture.

[0064] The amount of the deodorant composition immobilized on the substrate can be adjusted arbitrarily depending on the purpose, and is not particularly limited. Based on the unit area of ​​the substrate, the amount of the deodorant composition immobilized on the substrate is preferably 0.1 to 200 g / m. ２ The range is preferably 0.5 to 75 g / m ２ It is more preferable that the range is:

[0065] The amount of the carrier having aminooxyalkyl groups supported by chemical bonding to the substrate can be adjusted as desired depending on the purpose, and is not particularly limited. However, based on the unit area of ​​the substrate, the amount of the carrier having aminooxyalkyl groups supported by chemical bonding is preferably 0.09 to 180 g / m. ２ The range is preferably 0.45 to 68 g / m ２ It is more preferable that the range is:

[0066] The present invention will be described in more detail below with reference to examples, but these examples are provided to aid in the understanding of the present invention and are not intended to limit the scope of the present invention in any way. Unless otherwise specified, commercially available reagents and the like were used.

[0067] The analytical instruments and evaluation methods used in the examples are listed below.

[0068] <Acetaldehyde Capture Test> The deodorizing structure described below was sealed in a 5 L Tedlar bag, and then 3 L of nitrogen gas with an acetaldehyde concentration of approximately 14 ppm was added. After standing at room temperature for 2 hours, the entire 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 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: To a mixture of 19.94 g of silica gel (NIPGEL BY-400, manufactured by Tosoh Silica) with an average particle size of 4 μm and 173.4 g of toluene, a mixture of 8.08 g of a silane coupling agent represented by chemical formula (1a) and 43.35 g of toluene was added dropwise under a nitrogen stream, and the mixture was stirred at 25°C for 120 hours. 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 supported by chemical bonding (hereinafter referred to as "aminooxy group-supported support"). Elemental analysis of the obtained aminooxy group-supported support revealed that the aminooxyalkyl groups were contained at 1.4 mmol / g based on the weight of the aminooxy group-supported support.

[0070]

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

[0072] Synthesis Example 2: To a mixture of 16.88 g of silica gel (NIPGEL BY-001, manufactured by Tosoh Silica) with an average particle size of 14 μm, 44.87 g of toluene, and 16.88 g of distilled water, a mixture of 5.42 g of the silane coupling agent represented by the above chemical formula (1a) and 22.66 g of toluene was added dropwise under a nitrogen stream, and 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 the untreated silica gel (NIPGEL BY-001, manufactured by Tosoh Silica) and the aminooxy group-carrying carrier were measured. As a result, the untreated silica gel showed a peak at 970 cm －１ The silanol Si-O deformation vibration peak that was present near the aminooxy group-supported carrier disappeared. These results demonstrate that the surface hydroxyl groups of the silica gel are chemically modified by the silane coupling agent represented by the chemical formula (1a).

[0074] Synthesis Example 3: To a mixture of 16.88 g of silica gel (NIPSIL NS-T, manufactured by Tosoh Silica) with an average particle size of 21 μm, 45.00 g of toluene, and 16.88 g of distilled water, 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 under a nitrogen stream, and 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 support. Elemental analysis of the obtained aminooxy group-supported support revealed that it contained 1.4 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy group-supported support.

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

[0076] Synthesis Example 4 3.05 g of silica gel (NIPGEL BY-400, manufactured by Tosoh Silica) with an average particle size of 4 μm, 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 then stirred for 4 hours under heating and reflux in a nitrogen stream. 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 1.1 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy group-supported support.

[0077]

[0078] The IR spectra of the untreated silica gel (NIPGEL BY-400, manufactured by Tosoh Silica) and the aminooxy group-carrying carrier were measured. As a result, the IR spectrum of the silica gel was 970 cm －１ The silanol Si—O deformation vibration peak that was present near the aminooxy group-supported carrier disappeared. These results demonstrate that the surface hydroxyl groups of the silica gel are chemically modified with the silane coupling agent represented by the chemical formula (1b).

[0079] Synthesis Example 5 2.44 g of silica gel (NIPGEL BY-400, manufactured by Tosoh Silica) 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 for 4 hours under heating and reflux in a nitrogen stream. 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 0.9 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy group-supported support.

[0080]

[0081] The IR spectra of the untreated silica gel (NIPGEL BY-400, manufactured by Tosoh Silica) and the aminooxy group-carrying carrier were measured. As a result, the IR spectrum of the silica gel was 970 cm －１ The silanol Si—O deformation vibration peak that was present near the aminooxy group-supported carrier disappeared. These results demonstrate that the surface hydroxyl groups of the silica gel are chemically modified with the silane coupling agent represented by the chemical formula (1c).

[0082] Synthesis Example 6 1.83 g of silica gel (NIPGEL BY-400, manufactured by Tosoh Silica) with an average particle size of 4 μm, 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 then stirred for 4 hours under heating and reflux in a nitrogen stream. 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 the aminooxy alkyl group was contained in an amount of 0.8 mmol / g based on the weight of the aminooxy group-supported support.

[0083]

[0084] The IR spectra of the untreated silica gel (NIPGEL BY-400, manufactured by Tosoh Silica) and the aminooxy group-carrying carrier were measured. As a result, the IR spectrum of the silica gel was 970 cm －１The silanol Si—O deformation vibration peak that was present near the aminooxy group-supported carrier disappeared. These results demonstrate that the surface hydroxyl groups of the silica gel are chemically modified with the silane coupling agent represented by the chemical formula (1d).

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

[0086] Synthesis Example 8 3.05 g of powdered activated wood carbon (Osaka Gas Chemicals, Carborafine), 12.24 g of toluene, 0.46 g of distilled water, and 0.98 g of the silane coupling agent represented by the above-mentioned chemical formula (1a) were mixed and then stirred under nitrogen flow and heated to reflux for 4 hours. The resulting reaction solution was filtered, and the residue was dried at 120 ° C for 4 hours to obtain an aminoxy group-supported carrier. Elemental analysis of the obtained aminoxy group-supported carrier revealed that it contained 1.6 mmol / g of aminoxy alkyl groups relative to the weight of the aminoxy group-supported carrier.

[0087] Example 1 0.20 g of the aminooxy group-carrying carrier obtained in Synthesis Example 1, 0.24 g of an acrylic acid ester binder resin (Ficoat 70K, manufactured by Daiwa Chemical Industry Co., Ltd.), and 9.56 g of distilled water were mixed in a polyethylene container to obtain a deodorizing composition (deodorizing suspension composition).

[0088] 750 μL (0.75 g) of the obtained deodorizing composition (deodorizing suspension composition) was applied to a 10 cm long x 10 cm wide cloth fabric made of 100% polyester, and the fabric was dried at 150°C for 3 minutes using a hot air dryer (DRJ433DA, manufactured by Advantec Co., Ltd.), thereby obtaining a deodorizing structure in which the deodorizing composition was fixed.

[0089] Next, the obtained deodorizing structure was washed by repeatedly washing with water five times in accordance with the washing durability test method (JIS L 0217 103 method).

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

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

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

[0093] Example 4 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 1, except that a 100% cotton cloth fiber measuring 10 cm length x 10 cm width was used instead of the 100% polyester cloth fiber measuring 10 cm length x 10 cm width in Example 1.

[0094] Example 5 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 1, except that the amount of the deodorizing composition (deodorizing suspension composition) applied was changed from 750 μL (0.75 g) to 250 μL (0.25 g).

[0095] Example 6 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 1, except that the amount of acrylic acid ester binder resin (Ficoat 70K, manufactured by Daiwa Chemical Industry Co., Ltd.) was changed from 0.24 g to 0.08 g and the amount of distilled water was changed from 9.56 g to 9.72 g.

[0096] Example 7 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 1, except that the amount of acrylic acid ester binder resin (Ficoat 70K, manufactured by Daiwa Chemical Industry Co., Ltd.) was changed from 0.24 g to 0.02 g and the amount of distilled water was changed from 9.56 g to 9.78 g.

[0097] Example 8 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 1, except that 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 1 in Example 1 was changed to 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 2.

[0098] Example 9 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 1, except that 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 1 in Example 1 was changed to 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 3.

[0099] Example 10 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 1, except that 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 1 in Example 1 was changed to 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 4.

[0100] Example 11 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 1, except that 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 1 in Example 1 was changed to 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 5.

[0101] Example 12 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 1, except that 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 1 in Example 1 was changed to 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 6.

[0102] Example 13 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 1, except that 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 1 in Example 1 was changed to 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 7.

[0103] Example 14 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 1, except that 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 1 in Example 1 was changed to 0.20 g of the aminooxy group-supported carrier obtained in Synthesis Example 8.

[0104] Comparative Example 1 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 4, except that 0.24 g of acrylic acid ester binder resin (Ficoat 70K, manufactured by Daiwa Chemical Industry Co., Ltd.) was not added and the amount of distilled water was changed from 9.56 g to 9.80 g.

[0105] Comparative Example 2 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 4, except that 0.20 g of the aminooxy group-supporting carrier was not added and the amount of distilled water was changed from 9.56 g to 9.76 g.

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

[0107] Comparative Example 4 An odor-eliminating structure was produced and evaluated in the same manner as in Example 4, except that 10.0 g of an aqueous solution of adipic acid dihydrazide with a concentration of 3% by weight was used instead of 10.0 g of a odor-eliminating composition (odor-eliminating suspension composition) obtained by mixing 0.20 g of an aminooxy group-supporting carrier, 0.24 g of an acrylic acid ester binder resin (Ficoat 70K, manufactured by Daiwa Chemical Industry Co., Ltd.), and 9.56 g of distilled water.

[0108] Comparative Example 5 A deodorizing composition (deodorizing suspension composition) and a deodorizing structure were produced and evaluated in the same manner as in Example 1, except that 0.24 g of acrylic acid ester binder resin (Ficoat 70K, manufactured by Daiwa Chemical Industry Co., Ltd.) was not added and the amount of distilled water was changed from 9.56 g to 9.80 g.

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

[0110] Comparative Example 7 A deodorizing structure was produced and evaluated in the same manner as in Comparative Example 6, except that in Example 1, 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 (Ficoat 70K, manufactured by Daiwa Chemical Industry Co., Ltd.), and 9.56 g of distilled water was used instead of 10.0 g of a deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of a commercially available inorganic aldehyde scavenger (Kesmon NS750, manufactured by Toagosei Co., Ltd.), 0.08 g of an acrylic acid ester binder resin (Ficoat 70K, manufactured by Daiwa Chemical Industry Co., Ltd.).

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

[0112] The results of Examples 1 to 14 are shown in Table 1, and the results of 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 exhibited superior water resistance compared to existing deodorizing compositions.

[0113]

[0114]

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

Claims

1. A deodorizing composition comprising a carrier having an aminooxyalkyl group supported thereon by chemical bonding, and a binder resin.

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

3. A method for removing aldehyde, comprising exposing the deodorizing composition according to claim 1 or 2 to a space containing aldehyde, and bringing the aldehyde into contact with the deodorizing composition.

4. A deodorizing structure comprising a substrate having the deodorizing composition according to claim 1 or 2 adhered to its surface.

5. The odor-eliminating structure according to claim 4, wherein the substrate is a fiber, a sheet, wallpaper, a sponge, beads, wood, plywood, or gypsum board.

6. A method for removing aldehyde, comprising exposing the deodorizing structure according to claim 4 or 5 to an aldehyde-containing gas and bringing the aldehyde into contact with the deodorizing composition.