Deodorizing composition and deodorizing structure

Abstract

Provided is a deodorant composition that exhibits a more excellent aldehyde capturing effect than the prior art even when water washing, washing, is performed. A deodorant composition characterized by comprising a binder resin and a carrier having an aminooxyalkyl group supported thereon through chemical bonding is used.

Description

Technical Field

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

[0002] Aldehydes such as acetaldehyde and formaldehyde are representative odorous substances in the living environment. Because their odor threshold is extremely low, even very low concentrations can cause unpleasant smells. These aldehydes are known to be produced by synthetic resins, plywood, and cigarette smoke found indoors and in cars, contributing to sick house syndrome and sick car syndrome. Furthermore, these aldehydes are suspected of being carcinogenic, and daily exposure may harm health. Therefore, the Japanese Ministry of Health, Labour and Welfare has set indoor concentration limits of 0.03 ppm for acetaldehyde and 0.08 ppm for formaldehyde. Consequently, there is a search for methods to quickly and continuously remove aldehydes.

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

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 4-358536

[0007] Patent Document 2: Japanese Patent Application Publication No. 11-4879

[0008] Patent Document 3: Japanese Patent Application Publication No. 2018-108360 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] The methods described in the aforementioned patent documents 1 to 3 may not have sufficient capture efficiency, and their water resistance is insufficient. Therefore, there are problems such as the capture agent coated on the resin or fiber-based substrate dissolving and its performance decreasing due to water washing or rinsing.

[0011] In view of the background of the prior art described above, the object of the present invention is to provide an odor-capturing composition that exhibits superior aldehyde capture effect compared to the prior art even when subjected to water washing or rinsing.

[0012] Solution for solving the problem

[0013] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the specific deodorizing composition has excellent water resistance, thus completing the present invention.

[0014] That is, the present invention includes the following embodiments.

[0015] [1] An odor-deodorizing composition, characterized in that it comprises a binder resin and a carrier loaded with aminooxyalkyl groups by chemical bonding.

[0016] [2] According to the deodorizing composition described above [1], wherein the aforementioned carrier, which is chemically bonded with an aminooxyalkyl group, has any structure shown in the following general formula (2).

[0017]

[0018] (In the formula, R represents an alkyl group with 1 to 4 carbon atoms. X represents an alkoxy group with 1 to 4 carbon atoms. m' represents an integer from 0 to 2. n represents an integer from 1 to 12.)

[0019] [3] According to the deodorizing composition described above [2], wherein R is methyl and X is methoxy, ethoxy, propoxy or isopropoxy.

[0020] [4] The deodorizing composition according to [2] above, wherein n is 3 or 11.

[0021] [5] According to the deodorizing composition described in [1] or [2] above, wherein the aforementioned carrier loaded with aminooxyalkyl groups by chemical bonding is a reaction product of a compound of the following general formula (1) and an inorganic or polymeric carrier having hydroxyl groups on its surface.

[0022]

[0023] (In the formula, R represents an alkyl group with 1 to 4 carbon atoms. X represents an alkoxy group with 1 to 4 carbon atoms. m represents an integer from 0 to 2, and n represents an integer from 1 to 12.)

[0024] [6] According to the deodorizing composition described above [5], R is methyl and X is methoxy, ethoxy, propoxy or isopropoxy.

[0025] [7] The deodorizing composition according to [5] above, wherein n is 3 or 11.

[0026] [8] The deodorizing composition according to any one of [5] to [7] above, wherein the aforementioned inorganic carrier is silica gel, alumina, zeolite, magnesium oxide, titanium dioxide, zirconium oxide, cerium dioxide, diatomaceous earth, activated carbon, or hydroxyapatite.

[0027] [9] The deodorizing composition according to any one of [5] to [7] above, wherein the aforementioned inorganic carrier is silica gel.

[0028]

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

[0029]

[11] A method for removing aldehydes, characterized in that the deodorizing composition described in any one of [1] to

[10] is exposed to a space containing aldehydes, so that the aldehydes come into contact with the deodorizing composition.

[0030]

[12] An odor-deodorizing structure having a substrate on which the odor-deodorizing composition described in any one of [1] to

[10] is attached.

[0031]

[13] According to the deodorizing structure described above

[12] , the aforementioned substrate is fiber, sheet, wallpaper, sponge, bead, wood, plywood or gypsum board.

[0032]

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

[12] or

[13] is exposed to a gas containing aldehydes, so that the aldehydes come into contact with the deodorizing composition.

[0033] The effects of the invention

[0034] The present invention provides an aldehyde scavenger that exhibits excellent aldehyde scavenging effect even after water washing and has better water resistance than conventional formulations. Detailed Implementation

[0035] The present invention will now be described in detail.

[0036] The deodorizing composition of the present invention is characterized in that it comprises a binder resin and a carrier loaded with aminooxyalkyl groups by chemical bonding.

[0037] There are no particular limitations on the aforementioned carriers that are chemically bonded to aminooxyalkyl groups, and examples of carriers having any structure as shown in the following general formula (2) can be listed.

[0038]

[0039] (In the formula, R represents an alkyl group with 1 to 4 carbon atoms. X represents an alkoxy group with 1 to 4 carbon atoms. m' represents an integer from 0 to 2. n represents an integer from 1 to 12.)

[0040] There is no particular limitation on the alkyl group with 1 to 4 carbon atoms represented by R above, and examples include methyl, ethyl, propyl, isopropyl, butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, etc.

[0041] Regarding R, from the viewpoint of the efficiency of silane coupling reaction (described later), methyl is preferred.

[0042] There is no particular limitation regarding the alkoxy groups with 1 to 4 carbon atoms shown in X above. Examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, 2-methylpropoxy, 1-methylpropoxy, tert-butoxy, etc.

[0043] Regarding X, from the viewpoint of the efficiency of silane coupling reaction described later, it is preferably methoxy, ethoxy, propoxy or isopropoxy, more preferably methoxy or ethoxy, and even more preferably methoxy.

[0044] The aforementioned m' represents an integer from 0 to 2, and from the viewpoint of the efficiency of the silane coupling reaction described later, it is preferably 0 or 1.

[0045] The aforementioned n represents an integer from 1 to 12, but from the viewpoint of excellent aldehyde capture effect, it is preferably an integer from 3 to 12, and more preferably 3 or 11.

[0046] There are no particular limitations on the aforementioned carriers loaded with aminooxyalkyl groups by chemical bonding. For example, it is preferred to obtain a reaction product obtained by mixing a compound represented by the following general formula (1) (hereinafter also referred to as "silane coupling agent") with a carrier having hydroxyl groups on its surface (hereinafter also referred to as "silane coupling reaction").

[0047]

[0048] (In the formula, R represents an alkyl group with 1 to 4 carbon atoms. X represents an alkoxy group with 1 to 4 carbon atoms. m represents an integer from 0 to 2, and n represents an integer from 1 to 12.)

[0049] That is, the aforementioned carrier loaded with aminooxyalkyl groups by chemical bonding can be manufactured by reacting the above-mentioned silane coupling agent with a carrier having hydroxyl groups on its surface.

[0050] In the aforementioned silane coupling agents, the definitions and preferred ranges of R, X, and n are synonymous with the definitions and preferred ranges of R, X, and n in the aforementioned general formula (2).

[0051] In the aforementioned silane coupling agents, m represents an integer from 0 to 2. From the viewpoint of the efficiency of the silane coupling reaction, m is preferably 0 or 1.

[0052] The aforementioned silane coupling agent can be purchased commercially available or synthesized according to the methods described in Organic Preparations and Procedures International, vol.26, 1994, 111-113, Japanese Patent Application Publication No. 7-233132, and Tetrahedron Letters, Vol.46(14), 2005, 7973-7975.

[0053] The deodorizing composition of the present invention is characterized, as described above, having an aminooxyalkyl group (in general formulas (1) and (2) -(CH2)). n The group shown as -ONH2), with respect to the aminooxyalkyl group, part or all of which can form a chemically acceptable salt with an inorganic or organic acid.

[0054] The type of salt is not particularly limited, and examples include inorganic acid salts such as hydrochloride, hydrobromide, perchlorate, silicate, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate, or phosphate; or organic acid salts such as acetate, citrate, fumarate, maleate, trifluoromethanesulfonate, trifluoroacetate, benzoate, or p-toluenesulfonate. From the viewpoint of low cost, inorganic acid salts are preferred, and hydrochloride is even more preferred.

[0055] The loading amount of aminooxyalkyl groups in the aforementioned chemically bonded carrier can be adjusted arbitrarily according to the purpose, without particular limitation. Based on the unit weight of the chemically bonded carrier, it is preferably in the range of 0.01 to 10 mmol / g.

[0056] There are no particular limitations on the above-mentioned carriers; examples include polymeric carriers and inorganic carriers.

[0057] As a polymer carrier, there are no particular limitations, and examples include styrene-based polymers (such as polystyrene or cross-linked polystyrene), polyolefins (such as polyethylene or polypropylene), poly(halogenated olefins) (such as polyvinyl chloride or polytetrafluoroethylene), nitrile polymers (such as polyacrylonitrile), (meth)acrylic polymers (such as polymethyl methacrylate or polyethyl acrylate), and high molecular weight polysaccharides (such as cellulose, agarose, or dextran).

[0058] The aforementioned inorganic carriers are not particularly limited, and can be listed as examples such as silica gel, alumina, zeolite, magnesium oxide, titanium dioxide, zirconium oxide, cerium dioxide, diatomaceous earth, activated carbon, hydroxyapatite, etc.

[0059] Regarding the carrier, from the viewpoint of the efficiency of the above-mentioned silane coupling reaction, silica gel, alumina, zeolite, magnesium oxide, titanium dioxide, zirconium oxide, cerium dioxide, diatomaceous earth, activated carbon, cellulose or hydroxyapatite are preferred, and silica gel is even more preferred.

[0060] It should be noted that, regarding this carrier, a carrier having hydroxyl groups on its surface is preferred.

[0061] The shape of the aforementioned carrier is not particularly limited, and examples include spherical, granular, fibrous, particulate, monolithic, hollow fiber, or membrane-like structures. From the viewpoint of excellent aldehyde capture effect, spherical, membrane-like, granular, particulate, or fibrous structures are preferred, and spherical, granular, or particulate structures are more preferably preferred.

[0062] The particle size of the spherical, granular, or particulate carrier is preferably in the range of 0.1 μm to 10 mm, and from the viewpoint of good dispersibility in liquid, the average particle size is more preferably 1 μm to 100 μm.

[0063] The aforementioned carrier can be porous or non-porous, but from the perspective of excellent aldehyde capture effect, porous carrier is preferred.

[0064] When the aforementioned carrier is a porous carrier, the average pore diameter of the porous carrier is preferably 1 nm to 1 μm, and from the viewpoint of excellent aldehyde capture effect, it is more preferably 1 nm to 300 nm.

[0065] The binder resin contained in the deodorizing composition of the present invention is not particularly limited, and examples include acrylate resin, silicone resin, urethane resin, polyester resin, melamine resin, polypropylene resin, and fluororesin.

[0066] From the viewpoint of excellent adhesion to the aforementioned carrier loaded with aminooxyalkyl groups through chemical bonding and water resistance, the adhesive resin is preferably an acrylate resin, a silicone resin, or a urethane resin.

[0067] In the aforementioned deodorizing composition, the weight ratio of the carrier loaded with aminooxyalkyl groups by chemical bonding to the binder resin can be adjusted arbitrarily according to the purpose, without particular limitation. Preferably, the ratio of the carrier loaded with aminooxyalkyl groups by chemical bonding to the binder resin by weight is in the range of 1:1000 to 100:1, more preferably in the range of 1:100 to 100:1, and even more preferably in the range of 1:1.2 to 10:1.

[0068] The deodorizing composition of the present invention is characterized in that it comprises a binder resin and a carrier loaded with aminooxyalkyl groups by chemical bonding. This deodorizing composition is not particularly limited and can be manufactured by mixing the aforementioned carrier loaded with aminooxyalkyl groups by chemical bonding with the aforementioned binder resin. Alternatively, it can be manufactured by drying the deodorizing suspension composition described later.

[0069] The deodorizing composition of the present invention may further contain a solvent.

[0070] There are no particular limitations on the solvent used, and examples include water, ethanol, methanol, propanol, and acetonitrile. Among these, water is preferred from the viewpoint of its excellent aldehyde capture effect.

[0071] 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 aforementioned solvent is large, it becomes a suspension. This suspension is hereinafter referred to as the deodorizing suspension composition.

[0072] In the aforementioned deodorizing suspension composition, the total amount of the aforementioned carrier loaded with aminooxyalkyl groups by chemical bonding and the aforementioned binder resin to the weight ratio of the solvent can be adjusted arbitrarily according to the purpose, without particular limitation. Preferably, the total amount (by weight): solvent (by weight) is in the range of 1:1000 to 1:2, more preferably in the range of 1:100 to 1:4, and even more preferably in the range of 1:50 to 1:4.

[0073] There are no particular limitations on the aforementioned deodorizing suspension composition. For example, it can be manufactured by mixing and stirring the aforementioned carrier loaded with aminooxyalkyl groups by chemical bonding, the aforementioned binder resin, and the aforementioned solvent.

[0074] The method of using the aforementioned deodorizing composition or deodorizing suspension composition is not particularly limited. Examples include, for instance, directly contacting the deodorizing composition or deodorizing suspension composition with the source of odor (including aldehydes) or spraying it, or exposing it to a gas containing a substance that causes an unpleasant odor (including aldehydes) or spraying it.

[0075] There are no specific limitations on the sources of the aforementioned odors; examples include organic solvent-based adhesives, new building materials, and plywood.

[0076] By directly contacting the aforementioned deodorizing composition or deodorizing suspension composition with the aforementioned odor-generating source or by spraying it, the aforementioned odor substances are captured by the aforementioned deodorizing composition or deodorizing suspension composition. This reduces the amount of odor generated by the odor-generating source.

[0077] Furthermore, by exposing the aforementioned deodorizing composition or deodorizing suspension composition to a gas containing odor-causing substances (including aldehydes) that cause unpleasant odors, or by spraying it, the aforementioned odor-causing substances are captured by the aforementioned deodorizing composition or deodorizing suspension composition. This reduces the amount of odor in the aforementioned gas.

[0078] The substances that cause the aforementioned odor are not specifically limited, but can include, for example, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, isovaleraldehyde, hexanal, hexenal, nonenal, methyl isobutyl ketone, dimethyl ethyl ketone, ethyl acetate, acetic acid, propionic acid, n-butyric acid, n-valeric acid, isovaleric acid, methyl mercaptan, or ethyl mercaptan.

[0079] Other methods of using the aforementioned deodorizing composition or deodorizing suspension composition are not particularly limited. Examples include using the composition in a state where it is adhered to a substrate, and using a substrate with the aforementioned deodorizing composition or deodorizing suspension composition attached to its surface as a deodorizing structure.

[0080] The aforementioned deodorizing structure can be manufactured by coating or spraying the aforementioned deodorizing composition or deodorizing suspension composition onto a substrate.

[0081] Regarding the aforementioned deodorizing structure, by exposing it to a gas containing odor-causing substances (including aldehydes) that cause unpleasant odors, it is possible to capture the odor-causing substances in the gas and reduce the unpleasant odor of the gas.

[0082] The aforementioned substrate is not particularly limited and can be exemplified by materials such as fiber, sheet, wallpaper, sponge, beads, wood, plywood, or gypsum board.

[0083] The raw materials used for the aforementioned fibers, sheets, wallpapers, or sponges are not particularly limited, but can include, for example, polyester, polyamide, polyacrylonitrile, polypropylene, polyethylene, polyvinyl chloride, fluorinated resins, aromatic polyamide resins, sulfone resins, rayon, acetate, kapok, wool, silk, hemp, glass, carbon, ceramics, silicone resins, polyimide resins, natural rubber, polyurethane, etc.

[0084] The aforementioned deodorizing structures are not particularly limited and can include, for example, clothing, curtains, carpets, wall coverings, automotive interior materials, or furniture.

[0085] The amount of the deodorizing composition immobilized on the substrate can be adjusted arbitrarily according to the purpose and is not particularly limited. Based on the unit area of ​​the substrate, the deodorizing composition is preferably 0.1 to 200 g / m². 2 The range is more preferably 0.5–75 g / m2 The range.

[0086] The amount of the chemically bonded aminooxyalkyl support immobilized on the aforementioned substrate can be adjusted arbitrarily according to the purpose and is not particularly limited. Based on the unit area of ​​the aforementioned substrate, the chemically bonded aminooxyalkyl support is preferably 0.09 to 180 g / m². 2 The range is more preferably 0.45–68 g / m 2 The range.

[0087] Example

[0088] The present invention will now be described in more detail with reference to embodiments, but these are merely examples to aid in understanding the invention, and the invention is not limited to these embodiments in any way. It should be noted that commercially available reagents and other materials were used unless otherwise specified.

[0089] The following describes the analytical equipment and evaluation methods used in this embodiment.

[0090] <Acetaldehyde Capture Test>

[0091] After sealing the deodorizing structure (described later) into a 5L Tedra sampling bag, 3L of nitrogen gas with an acetaldehyde concentration of approximately 14ppm was added. After standing at room temperature for 2 hours, all the gas inside the Tedra sampling bag was adsorbed into a cartridge (Presep-C DNPH, manufactured by Fujifilm and Kouichi Chemicals Co., Ltd.) loaded with 2,4-dinitrophenylhydrazine (DNPH). The cartridge was treated with acetonitrile to dissolve the DNPH-aldehyde condensate. Then, the DNPH-aldehyde condensate was quantified using liquid chromatography (LC-2030C Plus, manufactured by Shimadzu Corporation), and the residual acetaldehyde concentration inside the Tedra sampling bag was calculated. The aldehyde capture rate [%) was then calculated according to the following formula.

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

[0093] Synthesis example 1

[0094] Under a nitrogen atmosphere, a mixture of 8.08 g of silane coupling agent (as shown in formula (1a)) and 43.35 g of toluene was added dropwise to a mixture of 19.94 g of silica gel (Tosoh Silica Corporation, NIPGELBY-400) with an average particle size of 4 μm and 173.4 g of toluene. 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 chemically bonded with aminooxyalkyl groups (hereinafter referred to as "aminooxy-supported support"). Elemental analysis of the obtained aminooxy-supported support showed that it contained 1.4 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy-supported support.

[0095]

[0096] The infrared absorption spectra (hereinafter referred to as IR spectra) of untreated silica gel (manufactured by Tosoh Silica Corporation, NIPGEL BY-400) and the aforementioned aminooxyl-based support were measured. The results showed that the untreated silica gel contained [a substance] at 970 cm⁻¹. -1 The nearby silanol Si-O angular vibration peak disappears in the aforementioned aminooxyl-supported carrier. Based on these results, it can be concluded that the surface hydroxyl groups of silica gel have been chemically modified using the silane coupling agent shown in the aforementioned chemical formula (1a).

[0097] Synthesis example 2

[0098] Under a nitrogen atmosphere, a mixture of 5.42 g of the silane coupling agent shown in formula (1a) and 22.66 g of toluene was added dropwise to a mixture of 16.88 g of silica gel (Tosoh Silica Corporation, NIPGELBY-001) with an average particle size of 14 μm, 44.87 g of toluene, and 16.88 g of distilled water. The mixture was stirred under reflux for 4 hours. The resulting reaction solution was filtered, and the residue was dried at 120 °C for 4 hours to obtain the aminooxy-supported carrier. Elemental analysis of the obtained aminooxy-supported carrier showed that it contained 1.5 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy-supported carrier.

[0099] The IR spectra of untreated silica gel (manufactured by Tosoh Silica Corporation, NIPGEL BY-001) and the aforementioned aminooxyl-based support were determined. The results showed that the untreated silica gel contained [a substance] at 970 cm⁻¹. -1 The nearby silanol Si-O angular vibration peak disappears in the aforementioned aminooxyl-supported carrier. Based on these results, it can be concluded that the surface hydroxyl groups of silica gel have been chemically modified using the silane coupling agent shown in the aforementioned chemical formula (1a).

[0100] Synthesis example 3

[0101] Under a nitrogen atmosphere, a mixture of 5.40 g of the silane coupling agent shown in formula (1a) and 22.72 g of toluene was added dropwise to a mixture of 16.88 g of silica gel (manufactured by Tosoh Silica Corporation, NIPSILNS-T) with an average particle size of 21 μm, 45.00 g of toluene, and 16.88 g of distilled water. The mixture was stirred under reflux for 4 hours. The resulting reaction solution was filtered, and the residue was dried at 120 °C for 4 hours to obtain the aminooxy-supported support. Elemental analysis of the obtained aminooxy-supported support showed that it contained 1.4 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy-supported support.

[0102] The IR spectra of untreated silica gel (manufactured by Tosoh Silica Corporation, NIPSIL NS-T) and the aforementioned aminooxyl-based support were determined. The results showed that the aforementioned silica gel contained [a substance] at 970 cm⁻¹. -1 The nearby silanol Si-O angular vibration peak disappears in the aforementioned aminooxyl-supported carrier. Based on these results, it can be concluded that the surface hydroxyl groups of silica gel have been chemically modified using the silane coupling agent shown in the aforementioned chemical formula (1a).

[0103] Synthesis example 4

[0104] 3.05 g of silica gel (Tosoh Silica Corporation, NIPGEL BY-400) with an average particle size of 4 μm, 12.22 g of toluene, 0.46 g of distilled water, and 0.90 g of the silane coupling agent shown in chemical formula (1b) were mixed and stirred under reflux for 4 hours under a nitrogen atmosphere. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain the aminooxy-supported carrier. Elemental analysis of the obtained aminooxy-supported carrier showed that it contained 1.1 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy-supported carrier.

[0105]

[0106] The IR spectra of untreated silica gel (manufactured by Tosoh Silica Corporation, NIPGEL BY-400) and the aforementioned aminooxyl-based support were determined. The results showed that the aforementioned silica gel contained [a substance] at 970 cm⁻¹. -1 The silanol Si-O angular vibration peaks nearby disappear in the aforementioned aminooxyl-supported carrier. Based on these results, it can be concluded that the surface hydroxyl groups of silica gel have been chemically modified using the silane coupling agent shown in the aforementioned chemical formula (1b).

[0107] Synthesis example 5

[0108] 2.44 g of silica gel (Tosoh Silica Corporation, 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 the silane coupling agent shown in chemical formula (1c) were mixed and stirred under reflux for 4 hours under a nitrogen atmosphere. The resulting reaction solution was filtered, and the residue was dried at 120 °C for 4 hours to obtain the aminooxy-supported support. Elemental analysis of the obtained aminooxy-supported support showed that it contained 0.9 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy-supported support.

[0109]

[0110] The IR spectra of untreated silica gel (manufactured by Tosoh Silica Corporation, NIPGEL BY-400) and the aforementioned aminooxyl-based support were determined. The results showed that the aforementioned silica gel contained [a substance] at 970 cm⁻¹. -1 The nearby silanol Si-O angular vibration peak disappears in the aforementioned aminooxyl-supported carrier. Based on these results, it can be concluded that the surface hydroxyl groups of silica gel have been chemically modified using the silane coupling agent shown in the aforementioned chemical formula (1c).

[0111] Synthesis example 6

[0112] 1.83 g of silica gel (Tosoh Silica Corporation, NIPGEL BY-400) with an average particle size of 4 μm, 7.32 g of toluene, 0.27 g of distilled water, and 0.93 g of the silane coupling agent shown in the following chemical formula (1d) were mixed and stirred under reflux for 4 hours under a nitrogen atmosphere. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain the aminooxy-supported support. Elemental analysis of the obtained aminooxy-supported support showed that it contained 0.8 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy-supported support.

[0113]

[0114] The IR spectra of untreated silica gel (manufactured by Tosoh Silica Corporation, NIPGEL BY-400) and the aforementioned aminooxyl-based support were determined. The results showed that the aforementioned silica gel contained [a substance] at 970 cm⁻¹. -1 The nearby silanol Si-O angular vibration peak disappears in the aforementioned aminooxyl-supported carrier. Based on these results, it can be concluded that the surface hydroxyl groups of silica gel have been chemically modified using the silane coupling agent shown in the aforementioned chemical formula (1d).

[0115] Synthesis Example 7

[0116] 3.05 g of powdered coconut shell activated carbon (manufactured by Osaka Gas Chemical Co., Ltd., Shirahi M), 12.30 g of toluene, 0.45 g of distilled water, and 0.97 g of the silane coupling agent shown in the aforementioned chemical formula (1a) were stirred under reflux for 4 hours under a nitrogen atmosphere. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain the aminooxy-supported carrier. Elemental analysis of the obtained aminooxy-supported carrier showed that it contained 1.4 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy-supported carrier.

[0117] Synthesis example 8

[0118] 3.05 g of powdered wood-based activated carbon (manufactured by Osaka Gas Chemical Co., Ltd., CARBORAFIN), 12.24 g of toluene, 0.46 g of distilled water, and 0.98 g of the silane coupling agent shown in the aforementioned chemical formula (1a) were mixed and stirred under reflux for 4 hours under a nitrogen atmosphere. The resulting reaction solution was filtered, and the residue was dried at 120°C for 4 hours to obtain the aminooxy-supported carrier. Elemental analysis of the obtained aminooxy-supported carrier showed that it contained 1.6 mmol / g of aminooxyalkyl groups relative to the weight of the aminooxy-supported carrier.

[0119] Example 1

[0120] 0.20 g of the aminooxyl-based support obtained in Synthesis Example 1, 0.24 g of acrylate-based binder resin (manufactured by Daiwa Chemical Industry Co., Ltd., FINE-COAT 70K) and 9.56 g of distilled water were mixed into a polyethylene container to obtain an odor-deodorizing composition (odor-deodorizing suspension composition).

[0121] 750 μL (0.75 g) of the deodorizing composition (deodorizing suspension composition) was coated onto 100% polyester fabric fibers with a length of 10 cm × width of 10 cm, and dried at 150 °C for 3 minutes using a hot air dryer (Advantech, DRJ433DA) to obtain a deodorizing structure with the deodorizing composition fixed thereon.

[0122] Next, the deodorizing structure was repeatedly washed with water five times according to the test method for washability (JIS L 0217 103 method), thereby washing the deodorizing structure.

[0123] Next, an acetaldehyde capture test was conducted using the deodorizing structures before and after washing.

[0124] Example 2

[0125] In Example 1, instead of 0.24g of acrylate-based binder resin (manufactured by Yamato Chemical Industry Co., Ltd., FINE-COAT70K), 0.24g of silicone-based binder resin (manufactured by Yamato Chemical Industry Co., Ltd., BITEK S-200L) was used. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the results were evaluated.

[0126] Example 3

[0127] In Example 1, instead of 0.24g of acrylate adhesive resin (manufactured by Yamato Chemical Industry Co., Ltd., FINE-COAT70K), 0.24g of urethane adhesive resin (manufactured by Yamato Chemical Industry Co., Ltd., U-30NP) was used, and otherwise the same procedure was followed as in Example 1.

[0128] Example 4

[0129] In Example 1, instead of 100% polyester fabric fibers with a length of 10cm x width of 10cm, 100% cotton fabric fibers with a length of 10cm x width of 10cm were used. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the composition was evaluated.

[0130] Example 5

[0131] In Example 1, the coating amount of the deodorizing composition (deodorizing suspension composition) was set from 750 μL (0.75 g) to 250 μL (0.25 g). Otherwise, the deodorizing composition (deodorizing suspension composition) and the deodorizing structure were manufactured and evaluated in the same manner as in Example 1.

[0132] Example 6

[0133] In Example 1, the amount of acrylate-based adhesive resin (manufactured by Daiwa Chemical Industry Co., Ltd., FINE-COAT 70K) was changed from 0.24g to 0.08g, and the amount of distilled water was changed from 9.56g to 9.72g. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the results were evaluated.

[0134] Example 7

[0135] In Example 1, the amount of acrylate-based adhesive resin (manufactured by Daiwa Chemical Industry Co., Ltd., FINE-COAT 70K) was changed from 0.24g to 0.02g, and the amount of distilled water was changed from 9.56g to 9.78g. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the results were evaluated.

[0136] Example 8

[0137] In Example 1, the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 1 was replaced with the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 2. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the results were evaluated.

[0138] Example 9

[0139] In Example 1, the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 1 was replaced with the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 3. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the results were evaluated.

[0140] Example 10

[0141] In Example 1, the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 1 was replaced with the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 4. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the results were evaluated.

[0142] Example 11

[0143] In Example 1, the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 1 was replaced with the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 5. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the results were evaluated.

[0144] Example 12

[0145] In Example 1, the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 1 was replaced with the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 6. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the results were evaluated.

[0146] Example 13

[0147] In Example 1, the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 1 was replaced with the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 7. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the results were evaluated.

[0148] Example 14

[0149] In Example 1, the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 1 was replaced with the 0.20 g of the aminooxy-supported carrier obtained in Synthesis Example 8. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the results were evaluated.

[0150] Comparative Example 1

[0151] In Example 4, 0.24 g of acrylate-based binder resin (manufactured by Daiwa Chemical Industry Co., Ltd., FINE-COAT70K) was not added, and the amount of distilled water was changed from 9.56 g to 9.80 g. Otherwise, the same procedure as in Example 4 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the results were evaluated.

[0152] Comparative Example 2

[0153] In Example 4, no aminooxygen-supported carrier (0.20 g) was added, and the amount of distilled water was changed from 9.56 g to 9.76 g. Otherwise, the same procedure as in Example 4 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the composition was evaluated.

[0154] Comparative Example 3

[0155] In Example 4, instead of using 10.0 g of the deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of an aminooxyl-supported carrier, 0.24 g of an acrylate-based binder resin (manufactured by Daiwa Chemical Industry Co., Ltd., FINE-COAT 70K), and 9.56 g of distilled water, 10.0 g of an aqueous solution of aminooxyacetic acid with a concentration of 3% by weight was used. Otherwise, the same procedure as in Example 4 was followed to manufacture the deodorizing structure and evaluate it.

[0156] Comparative Example 4

[0157] In Example 4, instead of using 10.0 g of the deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of an aminooxyl-supported carrier, 0.24 g of an acrylate-based binder resin (manufactured by Daiwa Chemical Industry Co., Ltd., FINE-COAT 70K), and 9.56 g of distilled water, 10.0 g of an aqueous solution of adipic acid dihydrazide with a concentration of 3% by weight was used. Otherwise, the same procedure as in Example 4 was followed to manufacture the deodorizing structure and evaluate it.

[0158] Comparative Example 5

[0159] In Example 1, 0.24 g of acrylate-based binder resin (manufactured by Daiwa Chemical Industry Co., Ltd., FINE-COAT70K) was not added, and the amount of distilled water was changed from 9.56 g to 9.80 g. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing composition (deodorizing suspension composition) and the deodorizing structure, and the composition was evaluated.

[0160] Comparative Example 6

[0161] In Example 1, instead of using 10.0 g of the deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of an aminooxygen-based support, 0.24 g of an acrylate-based binder resin (manufactured by Yamato Chemical Industry Co., Ltd., FINE-COAT 70K), and 9.56 g of distilled water, the same deodorizing composition (deodorizing suspension composition) was used.

[0162] Comparative Example 7

[0163] In Example 1, instead of using 10.0 g of the deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of an aminooxyl-based support, 0.24 g of an acrylate-based binder resin (manufactured by Yamato Chemical Industry Co., Ltd., FINE-COAT 70K), and 9.56 g of distilled water, 10.0 g of the deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of a commercially available inorganic aldehyde scavenger (manufactured by Toa Synthetic Co., Ltd., KESMON NS750), 0.08 g of an acrylate-based binder resin (manufactured by Yamato Chemical Industry Co., Ltd., FINE-COAT 70K), and 9.72 g of distilled water, the same procedure as in Example 1 was followed to manufacture the deodorizing structure and evaluate it.

[0164] Comparative Example 8

[0165] In Example 1, instead of using 10.0 g of the deodorizing composition (deodorizing suspension composition) obtained by mixing 0.20 g of an aminooxyl-based support, 0.24 g of an acrylate-based binder resin (manufactured by Yamato Chemical Industry Co., Ltd., FINE-COAT 70K), and 9.56 g of distilled water, the same deodorizing composition (deodorizing suspension composition) was used. Otherwise, the same procedure as in Example 1 was followed to manufacture the deodorizing structure and evaluate it.

[0166] The results of Examples 1-14 are shown in Table 1, and the results of Comparative Examples 1-8 are shown in Table 2. It is clear from Tables 1 and 2 that the deodorizing composition of the present invention exhibits superior water resistance compared to existing deodorizing compositions.

[0167] [Table 1]

[0168]

[0169] [Table 2]

[0170]

[0171] It should be noted that the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2021-054339, filed on March 26, 2021, are incorporated herein as disclosure of this invention.

Claims

1. An odor-eliminating composition characterized in that, which comprises a binder resin and a carrier loaded with an aminooxyalkyl group by chemical bonding, the carrier loaded with an aminooxyalkyl group by chemical bonding has any structure represented by the following general formula (2), in formula (2), 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.

2. The odor-eliminating composition of claim 1, wherein, R is a methyl group, and X is a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group.

3. The odor-eliminating composition of claim 1, wherein, n is 3 or 11.

4. The odor-eliminating composition of claim 1, wherein, the carrier loaded with an aminooxyalkyl group by chemical bonding is a reaction product of a compound represented by the following general formula (1) and an inorganic carrier or a high molecular carrier having a hydroxyl group on the surface, in formula (1), R represents an alkyl group having 1 to 4 carbon atoms; X represents an alkoxy group having 1 to 4 carbon atoms; m represents an integer of 0 to 2; and n represents an integer of 1 to 12.

5. The odor-eliminating composition of claim 4, wherein, R is a methyl group, and X is a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group.

6. The odor-eliminating composition of claim 4, wherein, n is 3 or 11.

7. The odor-eliminating composition of claim 4, wherein, the inorganic carrier is silica gel, alumina, zeolite, magnesium oxide, titanium oxide, zirconium oxide, cerium oxide, diatomite, activated carbon, or hydroxyapatite.

8. The odor-eliminating composition of claim 4, wherein, the inorganic carrier is silica gel.

9. The odor-eliminating composition according to any one of claims 1 to 8, wherein, the binder resin is an acrylate resin, a silicone resin, or a urethane resin.

10. A method for removing aldehydes, characterized by, exposing the odor-removing composition described in any one of claims 1 to 9 to a space containing an aldehyde, and allowing the aldehyde to contact the odor-removing composition.

11. An odor-removing structure having a base material to which the odor-removing composition described in any one of claims 1 to 9 is attached to the surface.

12. The deodorizing structure according to claim 11, wherein the base material is a fiber, a sheet, a wallpaper, a sponge, a bead, a wood, a plywood, or a plasterboard.

13. A method for removing aldehydes, characterized by, exposing the odor-removing structure described in claim 11 or 12 to a gas containing an aldehyde, and allowing the aldehyde to contact the odor-removing composition.

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