Polysiloxane, method for producing the same, and deodorant containing the same

Abstract

To provide a polysiloxane exhibiting an aldehyde-capturing effect, a method for producing the same, and a deodorant.SOLUTION: A polysiloxane of the general formula (1) in the figure is used. In the formula: R represents an organic group; Q represents an alkylene group that may have up to 20 carbon atoms and may have -O-, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -C(=O)NH-, -NH(C=O)-, -CH=CH-, or -C≡C-, where hydrogen atoms may be substituted with C1-C3 alkyl groups; and n represents a real number from 0 to 100.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to polysiloxane, a method for producing the same, and a deodorant containing the same.

Background Art

[0002] Aldehydes such as acetaldehyde and formaldehyde are typical odor substances in the living environment, and due to their extremely low odor thresholds, they cause unpleasant odors even at low concentrations. These aldehydes are generated from synthetic resins, plywood, tobacco smoke, etc. indoors and in automobiles, and are known to cause sick house syndrome and sick car syndrome. In addition, these aldehydes are also suspected of being carcinogenic, and if a person is exposed to them daily, there is a risk of harming health. Therefore, the Ministry of Health, Labour and Welfare has defined the indoor concentration guideline values as 0.03 ppm for acetaldehyde and 0.08 ppm for formaldehyde. Therefore, means for quickly and continuously removing aldehydes are required.

[0003] Lower aldehydes such as acetaldehyde and formaldehyde have low boiling points, so the capture efficiency is low with inorganic porous materials such as silica gel and activated carbon that are widely used as deodorants. Therefore, a method of capturing aldehydes by chemically reacting an aldehyde scavenger composed of a hydrazine derivative, an amine, an amino acid, a urea derivative, or the like with aldehydes has been disclosed (see, for example, Patent Documents 1 to 4).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, the methods described in these patent documents do not always have sufficient capture efficiency, and also do not have sufficient water resistance. Therefore, there are problems such as the capture agent applied to substrates such as resins and fibers eluting due to water washing or laundering, resulting in a decrease in performance.

[0006] The present invention has been made in view of the background of such prior art, and an object thereof is to provide a polysiloxane that exhibits an aldehyde capture effect even when washed with water or laundered, a method for producing the same, and a deodorant containing the same.

Means for Solving the Problems

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that a specific polysiloxane described below can solve the above problems, and have completed the present invention.

[0008] That is, the present invention includes the following embodiments.

[0009] [1] The following general formula (1)

[0010]

Chemical Formula

[0011] (In the formula, each R independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and the alkyl group may be substituted with one or more amino groups or ureido groups at any position. Q each independently represents -CH 2 -, -CH 2 CH 2 -, and -CH 2 -Ra-CH 2 - represents one or more groups selected from the group consisting of. Ra represents an alkylene group having 1 to 18 carbon atoms, -CH 2 -Ra-CH2 - Two -CH in 2 - CH sandwiched by - 2 - may each independently be replaced by -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, -C≡C-, and the hydrogen atom of the alkylene group may be replaced by an alkyl group having 1 to 3 carbon atoms. n represents a real number from 0 to 100.) An aminooxyalkyl group-containing polysiloxane having a structural unit represented by the formula and having a number average molecular weight of 500 to 10,000.

[0012] [2] In the general formula (1) above, the aminooxyalkyl group-containing polysiloxane according to [1] above, wherein R is each independently a methyl group, a 3-aminopropyl group, a (2-aminoethyl) 3-aminopropyl group, a 3-[2-(2-aminoethylamino)ethylamino]propyl group, a 3-ureidopropyl group, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, or a hydroxyl group.

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

[0014] [4] A method for producing the aminooxyalkyl group-containing polysiloxane according to any one of [1] to [3] above, wherein a compound represented by the following general formula (2) is polymerized in the presence of water.

[0015]

Chemical formula

[0016] (In the formula, R 1 each independently represents an alkyl group having 1 to 12 carbon atoms which may be substituted with one or more amino groups or ureido groups at any position, and R 2 each independently represents an alkoxy group having 1 to 4 carbon atoms. Q each independently represents -CH 2 -, -CH 2 CH 2-, and -CH 2 -Ra-CH 2 - represents one or more groups selected from the group consisting of. Ra represents an alkylene group having 1 to 18 carbon atoms, -CH 2 -Ra-CH 2 - Two of the -CH in 2 - The -CH sandwiched between 2 - may each independently be replaced by -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, -C≡C-, and the hydrogen atom of the alkylene group may be replaced by an alkyl group having 1 to 3 carbon atoms. m represents an integer of 0 to 2.) [5] A method for producing an aminooxyalkyl group-containing polysiloxane according to any one of [1] to [3] above, wherein a compound represented by the following general formula (2) and a compound represented by the following general formula (3) are copolymerized in the presence of water.

[0017] [Chemical formula]

[0018] (In the formula, R 1 each independently represents an alkyl group having 1 to 12 carbon atoms which may be substituted with one or more amino groups or ureido groups at any position, and R 2 each independently represents an alkoxy group having 1 to 4 carbon atoms. Q each independently represents -CH 2 -, -CH 2 CH 2 -, and -CH 2 -Ra-CH 2 - represents one or more groups selected from the group consisting of. Ra represents an alkylene group having 1 to 18 carbon atoms, -CH 2 -Ra-CH 2 - Two of the -CH in 2 - The -CH sandwiched between 2- may each independently be replaced by -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, -C≡C-, and the hydrogen atom of the alkylene group may be substituted by an alkyl group having 1 to 3 carbon atoms. m represents an integer of 0 to 2.)

[0019] [Chemical formula]

[0020] (In the formula, R 1 represents an alkyl group having 1 to 12 carbon atoms which may each independently be substituted by one or more amino groups or ureido groups at any position, and R 2 represents an alkoxy group having 1 to 4 carbon atoms each independently. m' represents an integer of 0 to 3.) [6] The production method of the aminooxyalkyl group-containing polysiloxane according to [5] above, wherein the ratio (molar ratio) of the molar amount of the compound represented by the general formula (2) to the molar amount of the compound represented by the general formula (3) is 100 or less in terms of the molar amount of the compound represented by the general formula (3) per 1 mol of the compound represented by the general formula (2).

[0021] [7] A deodorant containing the aminooxyalkyl group-containing polysiloxane according to any one of [1] to [3] above.

[0022] [8] A deodorant structure containing a substrate on which the aminooxyalkyl group-containing polysiloxane according to any one of [1] to [3] above is supported.

[0023] [9] The deodorant structure according to [8] above, wherein the substrate is a fibrous material, a sheet-like material, a bead-like material, a sponge-like material, or a board-like material.

[0024]

[10] A method for removing an aldehyde, which comprises bringing the deodorant according to [7] above into contact with the aldehyde.

[0025]

[11] A method for removing aldehydes, which comprises bringing the deodorizing structure described in [8] or [9] above into contact with an aldehyde.

Advantages of the Invention

[0026] A deodorant or a deodorizing structure containing an aminooxyalkyl group-containing polysiloxane according to one aspect of the present disclosure can rapidly and continuously capture aldehydes. As a result, it is effective in reducing aldehydes harmful to the human body and has the effect of improving the living environment.

Embodiments for Carrying Out the Invention

[0027] Hereinafter, the present invention will be described in detail. In this specification, "~" means a numerical range above and below including the numerical values at both ends thereof.

[0028] The aminooxyalkyl group-containing polysiloxane according to one aspect of the present disclosure has a structural unit represented by the above general formula (1).

[0029] In the above general formula (1), each R independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, which may be substituted with one or more amino groups or ureido groups at any position.

[0030] Examples of the alkyl group having 1 to 9 carbon atoms which may be substituted with one or more amino groups or ureido groups at any position include, but are not particularly limited to, methyl group, ethyl group, propyl group, 3-aminopropyl group, (2-aminoethyl)3-aminopropyl group, 3-[2-(2-aminoethylamino)ethylamino]propyl group, 3-ureidopropyl group, isopropyl group, butyl group, 2-methylpropyl group, 1-methylpropyl group, or tert-butyl group, etc.

[0031] The alkoxy group having 1 to 4 carbon atoms described above is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a 2-methylpropyloxy group, a 1-methylpropyloxy group, or a tert-butoxy group.

[0032] Among these, R is preferably a methyl group, a 3-aminopropyl group, a (2-aminoethyl)3-aminopropyl group, a 3-[2-(2-aminoethylamino)ethylamino]propyl group, a 3-ureidopropyl group, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, or a hydroxyl group in terms of excellent aldehyde capture.

[0033] Q is each independently a group selected from the group consisting of -CH 2 -, -CH 2 CH 2 -, and -CH 2 -Ra-CH 2 - (provided that two -CH 2 -Ra-CH 2 - in - may each independently be replaced by -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, -C≡C-, and the hydrogen atom of the alkylene group may be replaced by an alkyl group having 1 to 3 carbon atoms.). 2 - sandwiched between two -CH 2 - may each independently be replaced by -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, -C≡C-, and the hydrogen atom of the alkylene group may be replaced by an alkyl group having 1 to 3 carbon atoms.).

[0034] Regarding Q, it is not particularly limited, but specifically, structures represented by the following chemical formulas (Q-1) to (Q-95) etc. can be exemplified. In the following chemical formulas (Q-1) to (Q-95), the hydrogen atom on the alkylene group may be replaced by an alkyl group having 1 to 3 carbon atoms. * represents the bonding position in the general formula (1).

[0035]

Chemical formula

[0036] [Chemical formula]

[0037] The alkyl group having 1 to 3 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like.

[0038] In the above general formula (1), n represents a real number from 0 to 100. From the viewpoint of excellent aldehyde scavenging performance, n is preferably from 0 to 10, more preferably from 0 to 1, and even more preferably 0.

[0039] From the viewpoint of aldehyde scavenging ability, the number average molecular weight of the aminooxyalkyl group-containing polysiloxane is preferably from 500 to 50,000, more preferably from 500 to 20,000, still more preferably from 500 to 10,000, and even more preferably from 500 to 3,000. The number average molecular weight is the number average molecular weight measured by gel permeation chromatography (GPC).

[0040] The method for producing the aminooxyalkyl group-containing polysiloxane according to one aspect of the present disclosure is not particularly limited. Examples thereof include a method of polymerizing the compound represented by the above general formula (2) in the presence of water, and a method of copolymerizing the compound represented by the above general formula (2) and the compound represented by the above general formula (3) in the presence of water.

[0041] Regarding the compounds represented by the above general formula (2) and the above general formula (3), a mixture of a plurality of compounds mixed at an arbitrary ratio may be used.

[0042] In the compounds represented by the above general formula (2) and the above general formula (3), R 1 represents an alkyl group having 1 to 12 carbon atoms which may be substituted with one or more amino groups or ureido groups at an arbitrary position, and R 2 represents an alkoxy group having 1 to 4 carbon atoms.

[0043] The alkyl group having 1 to 12 carbon atoms which may be substituted with one or more amino groups or ureido groups at any of the above positions is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a 3-aminopropyl group, a (2-aminoethyl) 3-aminopropyl group, a 3-[2-(2-aminoethylamino)ethylamino]propyl group, a 3-ureidopropyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a 1-methylpropyl group, or a tert-butyl group.

[0044] The alkoxy group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a 2-methylpropyloxy group, a 1-methylpropyloxy group, or a tert-butoxy group.

[0045] In the compound represented by the above general formula (2), m represents an integer of 0 to 2.

[0046] In the compound represented by the above general formula (3), m' represents an integer of 0 to 3.

[0047] Among these, from the viewpoint of the efficiency of the polymerization reaction, R 1 is preferably a methyl group, a 3-aminopropyl group, a (2-aminoethyl) 3-aminopropyl group, a 3-[2-(2-aminoethylamino)ethylamino]propyl group, or a 3-ureidopropyl group, and R 2 is preferably a methoxy group, an ethoxy group, a propyloxy group, or an isopropyloxy group, m is preferably 0 or 1, and m' is preferably 0, 1, or 2.

[0048] The above polymerization reaction is carried out in the presence of water. First, the alkoxysilane moiety of the compound represented by the above general formula (2) and the above general formula (3) is hydrolyzed to generate hydroxy silane, and then intermolecular dehydration condensation occurs to proceed.

[0049] Although there is no particular limitation on the amount of water described above, from the viewpoint of the efficiency of the polymerization reaction, it is preferably 1 molar equivalent or more with respect to the total amount of the compound represented by the general formula (2) and the compound represented by the general formula (3).

[0050] The above polymerization reaction may be carried out using water as both a reaction accelerator and a solvent, or may be carried out by adding a solvent other than water as necessary.

[0051] The solvent other than water described above is not particularly limited, but a solvent having high compatibility with water is preferable. Specific examples include methanol, ethanol, propanol (the above are alcohol solvents), tetrahydrofuran, dioxane (the above are ether solvents), acetonitrile, dimethylformamide, dimethyl sulfoxide, 2-methylpyrrolidone, hexamethylphosphoramide, and the like.

[0052] The solvent other than water described above may be a single solvent or a mixed solvent.

[0053] The amount of the solvent other than water used is not particularly limited, but when the total amount of the compound represented by the general formula (2) and the compound represented by the general formula (3) is 1 part by weight, it is usually 1 to 100 parts by weight.

[0054] In the above polymerization reaction, the molar ratio of the compound represented by the general formula (2) to the compound represented by the general formula (3) can be arbitrarily adjusted according to the purpose and is not particularly limited. However, the molar amount of the compound represented by the general formula (3) with respect to 1 mole of the compound represented by the general formula (2) is preferably in the range of 0 to 1000, more preferably in the range of 0 to 100, still more preferably in the range of 0 to 10, even more preferably in the range of 0 to 4, and particularly preferably in the range of 0 to 2.

[0055] The above polymerization reaction is usually carried out in a temperature range of -20 to 200 °C, but from the viewpoint of production equipment, a temperature range of 0 to 150 °C is more preferable.

[0056] Since the reaction time of the polymerization reaction described above varies depending on the concentration of the compounds represented by the general formula (2) and the general formula (3) above, the amount of water used, the reaction temperature, etc., it is not particularly limited, but for example, it is several minutes to 14 days.

[0057] When copolymerizing the compound represented by the general formula (2) and the compound represented by the general formula (3), the copolymerization mode is not particularly limited, and examples thereof include random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, and the like.

[0058] The molecular shape of the aminooxy group-containing polysiloxane according to one aspect of the present disclosure is not particularly limited, and for example, it can take any molecular shape such as linear, branched, cyclic, etc.

[0059] After the polymerization reaction described above, a mixture containing the aminooxyalkyl group-containing polysiloxane described above is obtained. This mixture may be used as it is, or may be purified by operations such as distillation, reprecipitation, liquid separation, filtration, or column chromatography as necessary and then used.

[0060] The deodorant according to one aspect of the present disclosure contains the aminooxyalkyl group-containing polysiloxane described above.

[0061] In addition to the aminooxyalkyl group-containing polysiloxane described above, the deodorant may further contain a solvent, an acid, a base, a binder resin, a thickener, an antifoaming agent, a surfactant, an antibacterial agent, a preservative, etc.

[0062] The acid described above is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, hydrobromic acid, perchloric acid, silicic acid, tetrafluoroboric acid, hexafluorophosphoric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as acetic acid, citric acid, fumaric acid, maleic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, benzoic acid, and p-toluenesulfonic acid. As the acid described above, inorganic acids are preferable in terms of being inexpensive, and hydrochloric acid, sulfuric acid, and phosphoric acid are more preferable.

[0063] The above-mentioned base is not particularly limited. For example, inorganic bases such as ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, lithium citrate, sodium citrate, potassium citrate, rubidium citrate, cesium citrate, and organic bases such as polyethyleneimine, ethanolamine, diethanolamine, triethanolamine, tris(hydroxymethyl)aminomethane, ethylenediamine, diethylenetriamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, ethylenediamine-N,N,N’,N’-tetraethanol, 1,4-piperazinediethano, 1-(2,3-dihydroxypropyl)piperazine, 2-hydroxymethyltriethylenediamine, piperazine, N-(2-aminoethyl)piperazine, etc. may be mentioned. Among the above-mentioned bases, inorganic bases are preferable in terms of being inexpensive, and ammonia, sodium hydroxide, and potassium hydroxide are more preferable.

[0064] The above-mentioned solvent is not particularly limited. For example, water, methanol, ethanol, propanol, acetonitrile, etc. may be mentioned. Among these, from the viewpoint of safety to the human body, water or ethanol is preferable (hereinafter, the mixture of the deodorant and the solvent is referred to as the "deodorant solution").

[0065] The concentration of the aminooxyalkyl group-containing polysiloxane contained in the above-mentioned deodorant is not particularly limited, but the range of 0.1 to 50% by weight is preferable, and the range of 1 to 30% by weight is more preferable.

[0066] When the above-mentioned acid or base is contained in the above-mentioned deodorant, the content of the acid or base is not particularly limited, but -ONH 2For 1 mole of the group represented by the formula, the range of 0.001 to 10 molar equivalents is preferred, the range of 0.005 to 5 molar equivalents is more preferred, and the range of 0.01 to 2 molar equivalents is even more preferred.

[0067] When the above deodorant contains the binder resin, thickener, defoamer, surfactant, antibacterial agent, or preservative, the concentration of the binder resin, thickener, defoamer, surfactant, antibacterial agent, or preservative is not particularly limited. However, with the total amount of the above deodorant solution being 100% by weight, each independently, the range of 0.1 to 30% by weight is preferred, the range of 0.2 to 25% by weight is more preferred, and the range of 0.2 to 10% by weight is even more preferred.

[0068] The method for obtaining the above deodorant is not particularly limited. For example, a method of mixing and stirring the above aminooxyalkyl group-containing polysiloxane and a solvent can be mentioned.

[0069] The method of using the above deodorant is not particularly limited. For example, methods such as applying or spraying the deodorant onto a substrate, or spraying it onto an odor source can be mentioned.

[0070] The deodorant structure according to one aspect of the present disclosure includes a substrate on which the above aminooxyalkyl group-containing polysiloxane is supported.

[0071] The substrate in the above deodorant structure is not particularly limited. For example, fibrous materials, sheet-like materials, bead-like materials, sponge-like materials, board-like materials, etc. can be mentioned.

[0072] More specifically, for example, polyester fibers, polyamide fibers, polyacrylonitrile fibers, polypropylene fibers, polyethylene fibers, polyvinyl chloride fibers, fluorine fibers, aramid fibers, sulfone fibers, rayon, acetate, nylon, cotton, wool, silk, hemp, glass fibers, carbon fibers, ceramic fibers, mixed fibers thereof, woven fabrics made of these fibers, knitted fabrics made of these fibers, non-woven fabrics made of these fibers, yarns made of these fibers, ropes made of these fibers, strings made of these fibers, in addition to sheet-like materials, bead-like materials, sponge-like materials, wood, plywood, gypsum boards, etc. made of a material selected from the group consisting of polyester resins, polyamide resins, polyethylene resins, polypropylene resins, fluorine resins, silicone resins, polyimide resins, polyvinyl chloride resins, natural rubber, and synthetic rubber.

[0073] The deodorant structure described above can be used in any application according to the purpose and use. The use is not particularly limited, but for example, it can be used in applications such as for clothing, curtains, carpets, wall materials, automotive interior materials, furniture, household appliances, or filters.

[0074] The method for manufacturing the deodorant structure described above is not particularly limited, but for example, a method of supporting the aminooxyalkyl group-containing polysiloxane or the deodorant on a substrate can be mentioned.

[0075] The method for supporting the aminooxyalkyl group-containing polysiloxane or the deodorant on the substrate is not particularly limited, but for example, a method of applying the deodorant solution to the substrate described above, a method of immersing the substrate described above in the deodorant solution, etc. can be mentioned.

[0076] The amount of the aminooxyalkyl group-containing polysiloxane supported on the substrate can be arbitrarily adjusted according to the purpose and is not particularly limited, but the range of 0.01 to 100 g / m 2 is preferable, and 0.05 to 50 g / m 2The range is more preferable.

[0077] After the aminooxyalkyl group-containing polysiloxane or the deodorant is supported on a substrate, the obtained deodorant structure may be dried as needed. The drying conditions can be arbitrarily adjusted according to the purpose and are not particularly limited. For example, the temperature ranges from 0 to 200 °C and the time ranges from several minutes to 48 hours.

Examples

[0078] The present embodiment will be described in more detail based on the following examples. However, these are examples for helping the understanding of the present invention, and the present invention is not limited by these examples. In addition, commercially available products were used for the reagents and the like unless otherwise specified.

[0079] In addition, the following abbreviations were used for the compounds used in the examples.

[0080] O-[3-(triethoxysilyl)propyl]hydroxylamine: Si-1 3-(triethoxysilyl)propylamine: Si-2 N-(3-triethoxysilylpropyl)ethylenediamine: Si-3 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane: Si-4 3-(trimethoxysilyl)propylurea: Si-5 Tetraethoxysilane: TEOS O-octylhydroxylamine: OHA.

[0081]

Chemical formula

[0082] Example 1 <Preparation of deodorant> Si-1 (0.78 g, 3.29 mmol) and water (9.22 g) were mixed and stirred under reflux conditions (oil bath temperature 110 °C) for 20 hours to obtain a transparent solution containing an aminooxyalkyl group-containing polysiloxane. As a result of measuring the molecular weight of the obtained aminooxyalkyl group-containing polysiloxane by gel permeation chromatography (manufactured by Shimadzu Corporation, Prominence), the number average molecular weight (Mn) = 930, the weight average molecular weight (Mw) = 1100, and the dispersity (Mw / Mn) = 1.18 in terms of polyethylene glycol equivalent molecular weight.

[0083] <Preparation of deodorant structure> 0.1 g of the polysiloxane solution (hereinafter referred to as the carrier solution) obtained in the above reaction was mixed with 3.9 g of water to prepare a dilution solution. 0.25 g of this dilution solution was applied to a polyester non-woven fabric measuring 5 cm in length and 10 cm in width, and dried at 110 °C for 1 hour using a hot air dryer (manufactured by Advantec, DRJ433DA) to obtain a deodorant structure carrying an aminooxyalkyl group-containing polysiloxane (aminooxy group loading amount = 2 μmol).

[0084] <Acetaldehyde capture test> The above deodorant structure was sealed in a 5 L Tedlar bag, and then 2.5 L of nitrogen gas with an acetaldehyde concentration of 10 ppm was added to the Tedlar bag. After standing at 25 °C for 2 hours, the gas in the Tedlar bag was adsorbed onto a cartridge (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Presep-C DNPH) carrying 2,4-dinitrophenylhydrazine (DNPH). This cartridge was treated with acetonitrile to elute the DNPH-aldehyde condensate. Subsequently, the concentration of acetaldehyde in the eluate was quantified using a liquid chromatograph (manufactured by Shimadzu Corporation, LC-2030C Plus). Furthermore, the acetaldehyde capture rate was calculated from the following formula.

[0085] Acetaldehyde capture rate (%) = [(initial acetaldehyde concentration - residual acetaldehyde concentration) ÷ initial acetaldehyde concentration] × 100.

[0086] Examples 2 to 15 When preparing the deodorant, it was carried out in the same manner as in Example 1 except that the raw material composition, reaction temperature, or application amount of the diluent shown in Table 1 was changed. In the preparation of the deodorant structure, the amount of aminooxy groups supported on the fiber was 2 μmol, the same as in Example 1.

[0087] Comparative Example 1 When preparing the deodorant, it was carried out in the same manner as in Example 1 except that the raw materials were changed to Si-2 (0.73 g, 3.29 mmol) and water (9.27 g). In the preparation of the deodorant structure, the amount of amino groups supported on the fiber was 2 μmol.

[0088] Comparative Example 2 When preparing the deodorant, it was carried out in the same manner as in Example 1 except that the raw materials were changed to Si-3 (0.76 g, 3.29 mmol) and water (9.27 g). In the preparation of the deodorant structure, the amount of amino groups supported on the fiber was 4 μmol.

[0089] Comparative Example 3 When preparing the deodorant, it was carried out in the same manner as in Example 1 except that the raw materials were changed to Si-2 (0.77 g, 3.29 mmol) and water (9.27 g). In the preparation of the deodorant structure, the amount of amino groups supported on the fiber was 6 μmol.

[0090] Comparative Example 4 In Example 1, it was carried out in the same manner as in Example 1 except that the supporting solution was changed to an ethanol solution containing 7.8 wt% of Si-1. In the preparation of the deodorant structure, the amount of aminooxy groups supported on the fiber was 2 μmol, the same as in Example 1.

[0091] Comparative Example 5 In Example 1, it was carried out in the same manner as in Example 1 except that the supporting solution was changed to an ethanol solution containing 4.8 wt% of OHA. In the preparation of the deodorant structure, the amount of aminooxy groups supported on the fiber was 2 μmol, the same as in Example 1.

[0092] Comparative Example 6 0.1 g of an aqueous solution containing 5% by weight of ADH was mixed with 3.9 g of water to prepare a diluted solution. 0.29 g of this diluted solution was applied to a polyester nonwoven fabric measuring 5 cm in length and 10 cm in width, and dried at 110 °C for 1 hour using a hot air dryer (manufactured by Advantec, DRJ433DA) to obtain a deodorizing structure carrying ADH (ADH loading = 2 μmol, hydrazide group loading = 4 μmol).

[0093] Using the above deodorizing structure, an acetaldehyde capture test was carried out in the same manner as in Example 1, and the aldehyde capture rate was measured.

[0094] The results of Examples 1 to 15 and Comparative Examples 1 to 6 are shown in Table 1. As is clear from Table 1, the deodorants shown in the examples exhibited excellent aldehyde capture ability compared to the deodorants shown in the comparative examples.

[0095]

Table 1

[0096] Example 16 <Preparation of deodorizing structure> 0.1 g of the supported liquid obtained in Example 1 was applied to a polyester nonwoven fabric measuring 5 cm in length and 10 cm in width, and dried at 110 °C for 1 hour using a hot air dryer (manufactured by Advantec, DRJ433DA) to obtain a deodorizing structure carrying an aminooxyalkyl group-containing polysiloxane (aminooxy group loading = 35 μmol).

[0097] The above deodorizing structure was washed once or five times in accordance with the test method for washing durability (JIS L 0217 103 method).

[0098] An acetaldehyde capture test was carried out as follows for the deodorizing structure before washing, the deodorizing structure after one wash, and the deodorizing structure after five washes.

[0099] <Acetaldehyde capture test> The above deodorizing structure was enclosed in a 10 L Tedlar bag, and then 5 L of nitrogen gas with an acetaldehyde concentration of 10 ppm was added to the Tedlar bag. After standing at 25 °C for 2 hours, the acetaldehyde capture rate was calculated in the same manner as in Example 1.

[0100] Example 17 In Example 16, the same operations as in Example 16 were performed except that the substrate carrying the deodorant was changed to a cotton nonwoven fabric to produce a deodorizing structure (aminooxy group loading amount = 35 μmol).

[0101] For the above deodorizing structure, washing durability tests were carried out 1 or 5 times in accordance with the test method (JIS L 0217 103 method).

[0102] For the deodorizing structure before washing, after 1 wash, and after 5 washes, an acetaldehyde capture test was carried out in the same manner as in Example 16.

[0103] Example 18 In Example 16, the same operations as in Example 16 were performed except that the substrate carrying the deodorant was changed to a rayon nonwoven fabric to produce a deodorizing structure (aminooxy group loading amount = 35 μmol).

[0104] For the above deodorizing structure, washing durability tests were carried out 1 or 5 times in accordance with the test method (JIS L 0217 103 method).

[0105] For the deodorizing structure before washing, after 1 wash, and after 5 washes, an acetaldehyde capture test was carried out in the same manner as in Example 16.

[0106] Example 19 In Example 16, the same operations as in Example 16 were performed except that the substrate carrying the deodorant was changed to a polypropylene nonwoven fabric to produce a deodorizing structure (aminooxy group loading amount = 35 μmol).

[0107] Regarding the above-mentioned deodorant structure, washing durability tests were conducted 1 or 5 times in accordance with the test method for washing durability (JIS L 0217 103 method).

[0108] Regarding the deodorant structure before washing, the deodorant structure after 1 wash, and the deodorant structure after 5 washes, an acetaldehyde capture test was conducted in the same manner as in Example 16.

[0109] Example 20 In Example 16, a deodorant structure was prepared by performing the same operations as in Example 16, except that the substrate carrying the deodorant was changed to a nylon non-woven fabric (aminooxy group loading amount = 35 μmol).

[0110] Regarding the above-mentioned deodorant structure, washing durability tests were conducted 1 or 5 times in accordance with the test method for washing durability (JIS L 0217 103 method).

[0111] Regarding the deodorant structure before washing, the deodorant structure after 1 wash, and the deodorant structure after 5 washes, an acetaldehyde capture test was conducted in the same manner as in Example 16.

[0112] Comparative Example 7 In Example 16, a deodorant structure was prepared by performing the same operations as in Example 16, except that the carrier solution was changed to a 5% aqueous solution of adipic acid dihydrazide (adipic acid dihydrazide loading amount = 35 μmol).

[0113] Regarding the above-mentioned deodorant structure, washing durability tests were conducted 1 or 5 times in accordance with the test method for washing durability (JIS L 0217 103 method).

[0114] Regarding the deodorant structure before washing, the deodorant structure after 1 wash, and the deodorant structure after 5 washes, an acetaldehyde capture test was conducted in the same manner as in Example 16.

[0115] Comparative Example 8 In Comparative Example 7, an odor-removing structure was prepared by performing the same operations as in Comparative Example 5 except that the substrate carrying the deodorant was changed to a cotton nonwoven fabric (adipic acid dihydrazide loading = 35 μmol).

[0116] For the above-mentioned odor-removing structure, washing durability tests were carried out 1 or 5 times in accordance with the test method for washing durability (JIS L 0217 103 method).

[0117] For the odor-removing structure before washing, the odor-removing structure after 1 wash, and the odor-removing structure after 5 washes, an acetaldehyde capture test was carried out in the same manner as in Example 16.

[0118] Comparative Example 9 In Example 16, an odor-removing structure was prepared by performing the same operations as in Example 12 except that the carrier liquid was changed to a 5% aqueous solution of aminooxyacetic acid (aminooxyacetic acid loading = 35 μmol).

[0119] For the above-mentioned odor-removing structure, washing durability tests were carried out 1 or 5 times in accordance with the test method for washing durability (JIS L 0217 103 method).

[0120] For the odor-removing structure before washing, the odor-removing structure after 1 wash, and the odor-removing structure after 5 washes, an acetaldehyde capture test was carried out in the same manner as in Example 16.

[0121] Comparative Example 10 In Comparative Example 9, an odor-removing structure was prepared by performing the same operations as in Comparative Example 7 except that the substrate carrying the deodorant was changed to a cotton nonwoven fabric (aminooxyacetic acid loading = 35 μmol).

[0122] For the above-mentioned odor-removing structure, washing durability tests were carried out 1 or 5 times in accordance with the test method for washing durability (JIS L 0217 103 method).

[0123] For the odor-removing structure before washing, the odor-removing structure after 1 wash, and the odor-removing structure after 5 washes, an acetaldehyde capture test was carried out in the same manner as in Example 16.

[0124] The results of Examples 16 to 20 and Comparative Examples 7 to 10 are shown in Table 2. As is clear from Table 2, the deodorants shown in the examples exhibited excellent water resistance as compared with the deodorants shown in the comparative examples.

[0125] [Table 2]

Industrial Applicability

[0126] The aminooxyalkyl group-containing polysiloxane of the present disclosure rapidly and continuously captures aldehydes. As a result, it is possible to reduce odors derived from aldehydes and improve the living environment of humans.

Claims

1. The following general formula (1) 【Chemistry 1】 (In the formula, each R independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and the alkyl group may be substituted with one or more amino groups or ureido groups at any position. Each Q independently represents -CH ２ --, --CH ２ CH ２ - and -CH ２ -Ra-CH ２ Ra represents an alkylene group having 1 to 18 carbon atoms, -CH ２ -Ra-CH ２ Two -CH in - ２ - sandwiched between -CH ２ Each - may be independently replaced by -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-, and a hydrogen atom of the alkylene group may be replaced by an alkyl group having 1 to 3 carbon atoms. n represents a real number of 0 to 100. and a number average molecular weight of 500 to 10,000.

2. 2. The aminooxyalkyl group-containing polysiloxane according to claim 1, wherein, in the above general formula (1), each R is independently a methyl group, a 3-aminopropyl group, a (2-aminoethyl)3-aminopropyl group, a 3-[2-(2-aminoethylamino)ethylamino]propyl group, a 3-ureidopropyl group, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, or a hydroxyl group.

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

4. 2. The method for producing the aminooxyalkyl group-containing polysiloxane according to claim 1, which comprises polymerizing a compound represented by the following general formula (2) in the presence of water: 【Chemistry 2】 (In the formula, R １ each independently represents an alkyl group having 1 to 12 carbon atoms which may be substituted with one or more amino groups or ureido groups at any position; R ２ Each of Q independently represents an alkoxy group having 1 to 4 carbon atoms. ２ --, --CH ２ CH ２ - and -CH ２ -Ra-CH ２ Ra represents an alkylene group having 1 to 18 carbon atoms, -CH ２ -Ra-CH ２ Two -CH in - ２ - sandwiched between -CH ２ Each - may be independently replaced by -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-, and a hydrogen atom of the alkylene group may be replaced by an alkyl group having 1 to 3 carbon atoms. m represents an integer of 0 to 2.

5. 2. A method for producing the aminooxyalkyl group-containing polysiloxane according to claim 1, comprising copolymerizing a compound represented by the following general formula (2) with a compound represented by the following general formula (3) in the presence of water: 【Chemistry 3】 (In the formula, R １ each independently represents an alkyl group having 1 to 12 carbon atoms which may be substituted with one or more amino groups or ureido groups at any position; R ２ Each of Q independently represents an alkoxy group having 1 to 4 carbon atoms. ２ --, --CH ２ CH ２ - and -CH ２ -Ra-CH ２ Ra represents an alkylene group having 1 to 18 carbon atoms, -CH ２ -Ra-CH ２ Two -CH in - ２ - sandwiched between -CH ２ Each - may be independently replaced by -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-, and a hydrogen atom of the alkylene group may be replaced by an alkyl group having 1 to 3 carbon atoms. m represents an integer of 0 to 2. 【Chemistry 4】 (In the formula, R １ each independently represents an alkyl group having 1 to 12 carbon atoms which may be substituted with one or more amino groups or ureido groups at any position; R ２ each independently represents an alkoxy group having 1 to 4 carbon atoms; and m' represents an integer of 0 to 3.

6. 6. The method for producing an aminooxyalkyl group-containing polysiloxane according to claim 5, wherein the ratio (molar ratio) of the molar amount of the compound represented by the general formula (2) to the molar amount of the compound represented by the general formula (3) is 100 or less per 1 mole of the compound represented by the general formula (2).

7. A deodorant comprising the aminooxyalkyl group-containing polysiloxane according to any one of claims 1 to 3.

8. 4. A deodorizing structure comprising a substrate carrying the aminooxyalkyl group-containing polysiloxane according to claim 1.

9. 9. The odor eliminating structure according to claim 8, wherein the substrate is a fibrous material, a sheet-like material, a bead-like material, a sponge-like material, or a board-like material.

10. A method for removing aldehyde, comprising contacting the deodorant according to claim 7 with the aldehyde.

11. A method for removing aldehyde, comprising contacting the odor eliminating structure according to claim 8 with aldehyde.

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