Porous silica, deodorant, and method for manufacturing a deodorant

Abstract

Porous silica has at least one metal X selected from the group consisting of Mn, Cu, and Fe.

Description

Technology Field

[0001] The present invention relates to porous silica, a deodorizer, and a method for manufacturing a deodorizer. Background Technology

[0002] A wide variety of products are known as deodorizers. Among deodorizers, there are specific requirements for liquid deodorizers depending on their application. Furthermore, various types of deodorizers are known depending on the type of odor to be eliminated. For example, there is a specific requirement for deodorizers that target odors caused by sulfur-containing compounds (hereinafter referred to as sulfur-containing odors).

[0003] In relation to the above, for example, Patent Document 1 (Japanese Patent Publication No. 2003-261425) discloses a cysteamine-treated deodorizing agent for hair characterized by containing one or more types of divalent metal ions. Cysteamine is a sulfur-containing compound. The problem to be solved

[0004] The inventors examined ways to increase the deodorization efficiency of a liquid deodorizer for deodorizing sulfur-containing odors.

[0005] In other words, the objective of the present invention is to provide a liquid deodorizer capable of efficiently deodorizing sulfur-containing odors and a method for manufacturing the same. means of solving the problem

[0006] To solve the above problem, the present invention includes the following.

[0007] [1] Porous silica doped with metal X, which is Mn or Cu.

[0008] [2] Porous silica used in liquid deodorizers, having at least one metal X selected from the group consisting of Mn, Cu and Fe.

[0009] [3] The porous silica described in [2], in which the above metal X is doped into the above porous silica.

[0010] [4] Additionally, porous silica described in any of [1] to [3] having a metal different from the metal X above.

[0011] [5] Porous silica described in [4] having a metal Y selected from the group consisting of Al and Zr, which is different from the metal X above.

[0012] [6] Porous silica described in [4] or [5] having a metal Z selected from the group consisting of Co, Zn, Ag and Ca, which is different from the metal X above.

[0013] [7] Porous silica described in [4] having a structure with a chemical composition expressed by Formula 1 below.

[0014] (Equation 1) SiO2·aXO b / 2 ·cYO d / 2 ·eZO f / 2

[0015] (of Equation 1,

[0016] X represents the above metal X, and

[0017] Y represents a metal Y selected from the group consisting of A1 and Zr, and

[0018] Z represents a metal Z selected from the group consisting of Co, Zn, Ag, and Ca, and

[0019] a represents a number greater than 0 and less than or equal to 0.1, and

[0020] c and e represent numbers greater than or equal to 0 and less than or equal to 0.1, respectively, and

[0021] b, d, and f represent the valences of the metal X, the metal Y, and the metal Z, respectively.

[0022] [8] Porous silica described in any of [1] to [7], having a specific surface area of ​​500 m² / g or more.

[0023] [9] A powder deodorant containing porous silica of [1] to [8], which is a deodorant for permed hair.

[0024]

[10] A liquid deodorizer comprising porous silica and a solvent as described in any one of [1] to [8].

[0025]

[11] A liquid deodorizer described in

[10] , having a pH of 6 to 11.

[0026]

[12] A liquid deodorant for permed hair, as described in

[10] or

[11] .

[0027]

[13] A liquid deodorizer containing sulfur, as described in any of

[10] to

[12] .

[0028]

[14] Additionally, a liquid deodorant described in any of

[10] to

[13] containing a fragrance or hair protection ingredient.

[0029]

[15] A liquid deodorant described in any one of

[10] to

[14] , comprising water as the solvent.

[0030]

[16] A liquid deodorizer described in any of

[10] to

[15] , having a porous silica content of 0.001 to 50 mass%.

[0031]

[17] A method for manufacturing a deodorizer having a process of preparing porous silica having at least one metal X selected from the group consisting of Mn, Cu and Fe, and a process of mixing the porous silica with a solvent.

[0032] According to the present invention, a liquid deodorizer capable of efficiently deodorizing sulfur-containing odors and a method for manufacturing the same are provided. Specific details for implementing the invention

[0033] Hereinafter, embodiments of the present invention will be described. The deodorizing agent according to the present embodiment comprises a solvent and porous silica. The porous silica is dispersed in the solvent and contains at least one metal X selected from the group consisting of Mn, Cu, and Fe. By adopting such a composition, it becomes possible to efficiently deodorize sulfur-containing odors.

[0034] 1: Solvent

[0035] The solvent is not particularly limited as long as it disperses the porous silica without dissolving it. Preferably, a liquid containing water as a main component (e.g., 50 mass% or more) is used as the solvent.

[0036] The pH of the solvent is preferably 6 to 11, more preferably 6 to 9. If the pH is 6 or higher, there is no leaching of metal from the porous silica. If the pH is 11 or lower, the porous silica does not dissolve.

[0037] In addition, it is desirable for the solvent to have low viscosity. If the viscosity is low, the sulfur-containing compound to be deodorized can easily diffuse into the pores of the porous silica, thereby shortening the time required for deodorization. The viscosity of the solvent is, for example, 0.5 to 100 mPa / sec at 25°C.

[0038] 2: Porous silica

[0039] As described above, porous silica is dispersed in a solvent. The content of porous silica in the deodorizer is, for example, 0.001 to 50 mass%, preferably 0.1 to 10 mass%. If the content of porous silica is 0.001 mass% or more, a sufficient deodorizing effect can be obtained. If the content of porous silica is 50 mass% or less, the effect of maintaining fluidity can be obtained.

[0040] The specific surface area of ​​the porous silica is, for example, 500 m² / g or more, preferably 800 to 2000 m² / g, and more preferably 800 to 1600 m² / g. If the specific surface area of ​​the porous silica is 500 m² / g or more, a sufficient contact area between the metal X contained in the porous silica and the odor to be deodorized is secured, thereby achieving high deodorization efficiency. In addition, if the specific surface area is 2000 m² / g or less, strength to maintain the pore structure can also be secured.

[0041] The size of the pores formed in the porous silica should be large enough to allow solvent molecules and sulfur-containing compound molecules to pass through. For example, a pore diameter of 2 nm or more is sufficient.

[0042] Metal X contained in porous silica has the function of adsorbing sulfur-containing compounds. It is preferable that metal X be doped into the porous silica. "Doped" refers to a state in which metal X is incorporated into the positions of Si elements within the SiO4 framework of the silica.

[0043] The deodorization efficiency is higher when metal X is doped into porous silica compared to when metal X exists in granular form without doping. When metal X is doped, it is present across the entire surface of the porous silica. As a result, it is believed that a higher deodorization efficiency is achieved because the contact area between the odor and metal X increases compared to when metal X exists in granular form.

[0044] Furthermore, for example, if metal X is supported on porous silica as a solvent-soluble metal salt, it is conceivable that metal X may leach out into the solvent as metal ions during the use of the deodorizer. In some cases, it may become necessary to perform costly treatments, such as ion exchange, to prevent metal ions from leaking out into the wastewater, thereby creating a burden on wastewater treatment. In contrast, when metal X is doped into porous silica, the detachment of metal X from the porous silica is prevented, allowing for easy separation and recovery as a powder using a precipitation device, which can reduce the burden on wastewater treatment.

[0045] In addition, if metal X is included in a form doped into porous silica, the color intensity is reduced compared to when metal X is present alone.

[0046] The content of metal X in the porous silica is, for example, 0.01 to 10 mass%, preferably 0.1 to 5 mass%. If the content of metal X is 0.01 mass% or more, a sufficient deodorizing effect can be obtained. In addition, if it is 10 mass% or less, porous silica containing metal X can be easily synthesized.

[0047] As metal X, Mn or Cu is preferably used for its debridizing properties.

[0048] It is desirable that the porous silica contains a metal different from metal X.

[0049] As a metal different from metal X, metal Y can be cited, for example, to inhibit the hydrolysis of porous silica. As metal Y, for example, a metal selected from the group consisting of Al and Zr can be cited. It is preferable that metal Y be doped into the porous silica.

[0050] The hydrothermal durability of porous silica is enhanced by doping it with metal Y. This is thought to be because doping with metal Y inhibits the hydrolysis of the silica's siloxane framework, making it difficult for the pore structure to collapse.

[0051] The content of metal Y in the porous silica is, for example, 0.01 to 10 mass%, preferably 0.1 to 5 mass%. If the content of metal Y is 0.1 mass% or more, the effect of maintaining the specific surface area over time is obtained by inhibiting the hydrolysis of the siloxane backbone. If it is 10 mass% or less, a high specific surface area of ​​500 m² / g or more can be realized.

[0052] In addition, metal Z, which is different from metal X and has the function of removing odors other than sulfur-containing odors, may be included in the porous silica. As metal Z, at least one metal selected from the group consisting of Co, Zn, Ag, and Ca may be cited, and preferably Co, etc. When Co, etc. is included in the porous silica, deodorization of aldehydes and fatty acid odors can be expected in addition to sulfur-containing odors, so porous silica capable of deodorizing many odors at once can be obtained.

[0053] Metal Z may be "doped" into porous silica or "supported in porous silica as particles." Preferably, metal Z is doped into porous silica.

[0054] In addition, "supported in porous silica as particles" refers to a state in which a metal is supported in porous silica without being doped.

[0055] The content of metal Z in the porous silica is, for example, 0.01 to 10 mass%, preferably 0.1 to 5 mass%.

[0056] Specifically, it is desirable that the porous silica has at least a portion of the chemical structure represented by Formula 1 below.

[0057] (Equation 1): SiO2·aXO b / 2 ·cYO d / 2 ·eZO f / 2

[0058] Also, in Equation 1, X represents metal X.

[0059] Y represents metal Y.

[0060] Z represents the metal Z.

[0061] a represents a number greater than 0 and less than or equal to 0.1.

[0062] c and e represent numbers greater than or equal to 0 and less than or equal to 0.1, respectively.

[0063] b, d, and f represent the valences of metal X, metal Y, and metal Z, respectively.

[0064] In addition, to dope porous silica with metal X, metal Y, or metal Z, it is preferable to mix a water-soluble metal salt containing metal X, metal Y, or metal Z in an aqueous solution with the porous silica or its precursor during the manufacture of the porous silica. The doping of the metal can be confirmed by measuring the chemical bonding state using X-ray photoelectron spectroscopy or Raman spectroscopy, etc.

[0065] The deodorizer according to the present embodiment realizes the function of removing sulfur-containing odors in water by means of doped metal X.

[0066] Sulfur-containing compounds that are subject to deodorization are not particularly limited as long as they are deodorized by doped metal X, but examples include cysteamine, thioglycolic acid, cysteine, thiazolidine, methyl mercaptan, tert-butyl mercaptan, and hydrogen sulfide.

[0067] Cysteamine, thioglycolic acid, and cysteine, etc., are ingredients included, for example, in perming agents. Therefore, the deodorizing agent according to the present embodiment is suitably used to remove odors such as cysteamine attached to permed hair.

[0068] Generally, during a perm treatment, the hair is first coated with color. Subsequently, a chemical agent called perm solution 1 is applied to the hair. Perm solution 1 contains a reducing agent that breaks the cystine bonds of the hair. Specifically, examples of such reducing agents include cysteamine, thioglycolic acid, and cysteine.

[0069] When the cystine bonds are broken, the hair is suitable for a shape wrapped in color.

[0070] Afterwards, the second perm solution is applied to the hair. The second perm solution contains an oxidizing agent. The cystine bonds that were severed by the action of the oxidizing agent are re-bonded. As a result, the shape of the hair is fixed in a form wrapped in color.

[0071] The deodorizing agent according to the present embodiment may be used, for example, as an ingredient incorporated into the perm solution described above. Alternatively, it may be used as a chemical agent applied to the hair separately from the perm solution. For example, the deodorizing agent according to the present embodiment may be incorporated into conditioners, hair sprays, and hair waxes applied to the hair after perming treatment.

[0072] The deodorant applied to the hair may be washed off after it has performed its deodorizing function, or it may not need to be washed off.

[0073] The deodorizer may contain fragrance or hair protection ingredients. It is preferable that the fragrance or hair protection ingredients exist within porous silica. When the fragrance or hair protection ingredients are included, if the deodorizer is applied to the hair and left to stand, the fragrance or hair protection ingredients are sustained-released. Accordingly, not only can it deodorize simple sulfur-containing odors, but it can also achieve other functions, such as deodorizing body odor or scalp odor with fragrance, and protecting the hair.

[0074] To incorporate fragrances or hair protection ingredients into porous silica, methods include adding porous silica to a solution in which these ingredients are dispersed, stirring, and then distilling off the solvent by vacuum drying.

[0075] The deodorizing agent according to the present embodiment is not necessarily used only for deodorizing hair after perming treatment, but can also be used for other purposes. For example, food waste contains sulfur-containing odors. Therefore, the deodorizing agent according to the present embodiment is also suitable for use as a deodorizing spray for food waste.

[0076] As explained above, according to the deodorizing agent of the present embodiment, since porous silica doped with metal X is dispersed in a solvent, sulfur-containing odors can be efficiently deodorized.

[0077] In particular, since porous silica is used, metal X, which exhibits a deodorizing function, can be uniformly dispersed in a solvent, and as a result, the chemical reaction rate between metal X and a sulfur-containing compound can be improved.

[0078] In addition, porous silica itself has deodorizing performance against odors other than sulfur-containing odors (acidic and basic odors). Therefore, the deodorizing agent according to the present embodiment is capable of deodorizing odors other than sulfur-containing odors.

[0079] In addition, porous silica is easily attached to hair. Therefore, when the deodorizing agent according to the present embodiment is applied to hair, the porous silica adheres to the hair. Accordingly, it becomes possible to exert the deodorizing action by metal X more reliably.

[0080] 3: Manufacturing Method

[0081] The deodorizing agent according to the present embodiment can be obtained by manufacturing porous silica and then dispersing the porous silica in a solvent.

[0082] In addition, porous silica can be manufactured by a method including, for example, the following process.

[0083] (A) A process of preparing a surfactant solution by mixing a solvent, a surfactant, and a compound for a metal X dope containing metal X.

[0084] (B) A process of adding a silica source to a surfactant solution to generate micelles with accumulated silica sources on the surface

[0085] (C) Process of condensing accumulated silica sources

[0086] (D) Process of recovering micelles and calcining after the condensation process

[0087] Below, each process is explained in detail.

[0088] (A): Preparation of surfactant solution

[0089] First, a surfactant solution is prepared by adding a surfactant and a compound for metal X dope to a solvent. The surfactant solution is preferably stirred at room temperature or higher and 200°C or lower for 30 minutes or more and 10 hours or less. Accordingly, the surfactant forms micelles.

[0090] For example, water can be used as a solvent. In addition, a mixture of water and an organic solvent such as ethanol or toluene may be used as a solvent.

[0091] The amount of surfactant added is preferably 50 to 400 mmol / L, more preferably 50 to 150 mmol / L.

[0092] Alternatively, the amount of surfactant added is 0.01 to 5.0 moles, preferably 0.05 to 1.0 moles, per 1 mole of silica source added later.

[0093] As for the surfactant, it is not particularly limited, and all cationic, anionic, and nonionic surfactants can be used.

[0094] Preferably, the surfactant is neutral or cationic, and more preferably, is an alkylammonium salt. The alkylammonium salt preferably has 8 or more carbon atoms, and considering the ease of industrial availability, it is more preferable that it has 12 to 18 carbon atoms. Examples of alkylammonium salts include hexadecyltrimethylammonium chloride, cetyltrimethylammonium bromide, stearyltrimethylammonium bromide, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, dodecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, didodecyldimethylammonium bromide, ditetradecyldimethylammonium bromide, didodecyldimethylammonium chloride, ditetradecyldimethylammonium chloride, etc. These surfactants may be used alone, or two or more may be used in combination.

[0095] A compound for metal X doping is a material that serves as a source of metal X to be doped into porous silica. As the compound for metal X doping, a water-soluble compound containing metal X is preferably used. More preferably, chlorides, nitrates, and sulfates of metal X are used.

[0096] For example, if metal X is iron, iron(III) chloride, etc. is added as a compound for the metal X dope.

[0097] For example, if metal X is copper, copper nitrate (II) is added as a compound for the metal X dope.

[0098] For example, if metal X is manganese, manganese chloride (II) is added as a compound for the metal X dope.

[0099] Compounds for metal X dopes may be used alone or in combination of two or more types.

[0100] The amount of compound added for the metal X dope is, for example, 0.001 to 0.5 moles, preferably 0.01 to 0.1 moles, per 1 mole of silica source.

[0101] (B): Addition of silica source

[0102] Next, silica source is added to the surfactant solution.

[0103] The silica source is not particularly limited as long as it serves as a raw material for silica, but examples include tetraethoxysilane, tetramethoxysilane, tetra-n-butoxysilane, and sodium silicate. These silica sources may be used individually or in combination of two or more types. The silica source is preferably an alkoxysilane. The silica source is more preferably a tetraethoxysilane. Organic functional groups on silicon atoms are lost through hydrolysis and therefore do not affect the structure of the composite. However, if the volume of the organic functional groups is large, the hydrolysis rate slows down, and the synthesis time becomes long.

[0104] In addition, when sodium silicate is used alone or in combination as a silica source, the surfactant solution is heated and refluxed at 200°C or lower for 20 to 2 hours.

[0105] The amount of silica source added is not particularly limited, but is, for example, 0.2 to 1.8 mol / L. Or, if the solvent contains water, the concentration of the silica source is, for example, 0.001 to 0.05 mol per 1 mol of water.

[0106] (C): Condensation of silica source

[0107] Next, the silica source is condensed. Specifically, the pH of the solution is increased or decreased until the silica source is condensed. For example, the silica source can be condensed by adding a basic aqueous solution and stirring. Stirring is performed, for example, for at least one hour. Upon addition of the basic aqueous solution, the silica source accumulated on the surface of the micelle undergoes dehydration condensation to form a silica wall.

[0108] Examples of basic aqueous solutions include aqueous solutions of sodium hydroxide, sodium carbonate, and ammonia. The basic aqueous solution is preferably an aqueous solution of sodium hydroxide. These basic aqueous solutions may be used alone or in combination of two or more types. The basic aqueous solution is added so that, immediately after addition, the pH is preferably 8 to 14, and more preferably 9 to 11. The addition of the basic aqueous solution accelerates the dehydration condensation reaction of the silica source.

[0109] As a result, the surface tension of the condensation portion increases, causing the silica walls to become spherical, and the spheres become bonded in multiple layers, leading to spinodal decomposition (phase separation). These structures are frozen by chemical crosslinking.

[0110] In addition, silica source has the property of condensing even at low pH. Therefore, silica source can be condensed by adding an acidic aqueous solution, rather than a basic aqueous solution.

[0111] (D): Recovery and calcination of micelles

[0112] Next, micelles are recovered from an aqueous solution as a precursor. Specifically, micelles precipitate when a silica source is condensed. Thus, micelles are recovered as a precursor by filtering the precipitate. The recovered precursor is dried. After drying, the precursor is calcined to remove organic components contained in the precursor. That is, the surfactant constituting the micelles is removed. Accordingly, porous silica having pores is formed. Furthermore, calcination is performed at a temperature above the decomposition temperature of the surfactant. The calcination temperature is, for example, 400 to 600°C.

[0113] The porous silica obtained by the above method is doped with metal X derived from a compound for metal X doping. That is, porous silica doped with metal X is obtained.

[0114] In addition, the above method describes an example in which a compound for metal X doping is added in process (A). However, the compound for metal X doping does not necessarily have to be added in process (A), and may be added to the solution at any stage prior to calcination in process (D). When the accumulated silica source and the compound for metal X doping are mixed in the solution, metal X derived from the compound for metal X doping is introduced into the silica source, and porous silica doped with metal X is obtained.

[0115] Additionally, when manufacturing porous silica containing metal Y and / or metal Z in addition to metal X, it is preferable to add a compound for the metal Y dope or a compound for the metal Z feed at any step prior to process (D).

[0116] The compound for the metal Y dope and the compound for the metal Z supply are substances that serve as sources of metal Y and metal Z, respectively. As the compound for the metal Y dope and the compound for the metal Z supply, water-soluble compounds containing metal Y or Z are preferably used. More preferably, chlorides, nitrates, and sulfates of metal Y or metal Z are used.

[0117] For example, if metal Y is aluminum, aluminum chloride, etc., is added as a compound for the metal Y dope.

[0118] For example, when metal Y is Zr, zirconium oxychloride, etc. is added as a compound for metal Y dope.

[0119] For example, if metal Z is cobalt, cobalt nitrate, etc., is added as a compound to supply metal Z.

[0120] For example, if the metal Z is Zn, zinc nitrate, etc., is added as a compound to supply the metal Z.

[0121] For example, if metal Z is Ag, silver nitrate, etc., is added as a compound to supply metal Z.

[0122] For example, if metal Z is Ca, calcium carbonate, etc., is added as a compound to supply metal Z.

[0123] The compounds for metal Y dope and metal Z supply may be used alone or in combination of two or more types.

[0124] The amount of compound for metal Y dope and compound for metal Z supply added is, for example, 0.001 to 0.5 moles, preferably 0.01 to 0.1 moles per 1 mole of silica source.

[0125] (Example)

[0126] Embodiments of the present invention will be described below. However, the present invention is not to be interpreted as being limited to these embodiments.

[0127] Deodorizing agents according to Examples 1 to 8 and Comparative Examples 1 to 6 were prepared. The specific surface area, metal content, and cysteamine adsorption amount of the obtained deodorizing agents were measured. The preparation and measurement methods for each example and comparative example are as follows.

[0128] Example 1

[0129] To water as a solvent, hexadecyltrimethylammonium chloride as a surfactant, manganese chloride as a compound for metal X dope, and aluminum chloride as a compound for metal Y dope were added and stirred at 100°C for 1 hour. After cooling the aqueous solution to room temperature, tetraethoxysilane was added as a silica source and stirred. Subsequently, sodium hydroxide was added as a condensation catalyst and stirred. The amount of each compound added was the following amounts per mole of tetraethoxysilane.

[0130] Surfactant (Hexadecyltrimethylammonium chloride): 0.225 mol

[0131] Compound for Metal X Dope (Manganese Chloride): 0.0118 mol

[0132] Compound for Metal Y Dope (Aluminum Chloride): 0.0482 mol

[0133] Water: 125 moles

[0134] Sodium hydroxide: 0.195 mol

[0135] The solid product from the obtained suspension was filtered and separated, dried, and then calcined to remove organic components to obtain porous silica. This was used as the deodorizing agent according to Example 1.

[0136] Example 2

[0137] Before adding the silica source, cobalt nitrate was additionally added as a compound for supplying metal Z. The amount of each compound added was set to the following amounts per 1 mole of tetraethoxysilane.

[0138] Surfactant (Hexadecyltrimethylammonium chloride): 0.225 mol

[0139] Compound for Metal X Dope (Manganese Chloride): 0.0118 mol

[0140] Compound for Metal Y Dope (Aluminum Chloride): 0.0241 mol

[0141] Compound for metal Z supply (cobalt nitrate): 0.011 mol

[0142] Water: 125 moles

[0143] Sodium hydroxide: 0.195 mol

[0144] A deodorizing agent for Example 2 was prepared in the same manner as Example 1 except for the other details.

[0145] Example 3

[0146] Copper nitrate was used as a compound for the metal X dope. The amount of each compound added was set to the following amounts per 1 mole of tetraethoxysilane.

[0147] Surfactant (Hexadecyltrimethylammonium chloride): 0.225 mol

[0148] Compound for Metal X Dope (Copper Nitrate): 0.0204 mol

[0149] Compound for Metal Y Dope (Aluminum Chloride): 0.0482 mol

[0150] Water: 125 moles

[0151] Sodium hydroxide: 0.195 mol

[0152] A deodorant for Example 3 was prepared in the same manner as in Example 1, except for the other details.

[0153] Example 4

[0154] Copper nitrate was used as the compound for the metal X dope. Aluminum chloride and zirconium oxychloride were used as the compounds for the metal Y dope. Cobalt nitrate was added as the compound for the metal Z supply. The amount of each compound added was set as follows per 1 mole of tetraethoxysilane.

[0155] Surfactant (Hexadecyltrimethylammonium chloride): 0.225 mol

[0156] Compound for Metal X Dope (Copper Nitrate): 0.0102 mol

[0157] Compound for Metal Y Dope (Aluminum Chloride): 0.0478 mol

[0158] Compound for metal Y dope (zirconium oxychloride): 0.021 mol

[0159] Compound for metal Z supply (cobalt nitrate): 0.0116 mol

[0160] Water: 125 moles

[0161] Sodium hydroxide: 0.282 mol

[0162] A deodorizing agent for Example 4 was prepared in the same manner as Example 1 except for the other details.

[0163] Example 5

[0164] Copper nitrate was used as the compound for the metal X dope. Aluminum chloride and zirconium oxychloride were added as compounds for the metal Y dope. The amount of each compound added was set as follows per 1 mole of tetraethoxysilane.

[0165] Surfactant (Hexadecyltrimethylammonium chloride): 0.225 mol

[0166] Compound for Metal X Dope (Copper Nitrate): 0.0102 mol

[0167] Compound for Metal Y Dope (Aluminum Chloride): 0.0498 mol

[0168] Compound for metal Y dope (zirconium oxychloride): 0.022 mol

[0169] Water: 125 moles

[0170] Sodium hydroxide: 0.282 mol

[0171] A deodorizing agent for Example 5 was prepared in the same manner as Example 1 except for the other details.

[0172] Example 6

[0173] Iron chloride was added as a compound for metal X dope. The amount of each compound added was set to the following amounts per 1 mole of tetraethoxysilane.

[0174] Surfactant (Hexadecyltrimethylammonium chloride): 0.225 mol

[0175] Compound for Metal X Dope (Iron Chloride): 0.0537 mol

[0176] Compound for Metal Y Dope (Aluminum Chloride): 0.0241 mol

[0177] Water: 125 moles

[0178] Sodium hydroxide: 0.195 mol

[0179] A deodorizing agent for Example 6 was prepared in the same manner as Example 1 except for the other details.

[0180] Example 7

[0181] Oxine manganese was added as a compound for the metal X dope. No compound for the metal Y dope was added. The amount of each compound added was set to the following amounts per 1 mole of tetraethoxysilane.

[0182] Surfactant (Hexadecyltrimethylammonium chloride): 0.225 mol

[0183] Compound for Metal X Dope (Oxine Manganese): 0.0118 mol

[0184] Water: 125 moles

[0185] Sodium hydroxide: 0.195 mol

[0186] A deodorizing agent for Example 7 was prepared in the same manner as Example 1 except for the other details.

[0187] Example 8

[0188] Surfactants and compounds for the metal Y dope were not added. Copper nitrate was used as the compound for the metal X dope. Nitric acid was used as the condensation catalyst. The amount of each compound added was set to the following amounts per 1 mole of tetraethoxysilane.

[0189] Compound for Metal X Dope (Copper Nitrate): 0.0102 mol

[0190] Water: 10 moles

[0191] Nitric acid: 0.1 mol

[0192] A deodorizing agent for Example 8 was prepared in the same manner as Example 1 except for the other details.

[0193] Comparative Example 1

[0194] Manganese(IV) oxide powder manufactured by Wako Junyaku (Wako Grade 1, catalog code 138-09675) was prepared as Comparative Example 1.

[0195] Comparative Example 2

[0196] A powder obtained by dissolving cobalt chloride and manganese nitrate in water in a molar ratio of 1:1, heating at 100°C to volatilize the water, and then calcining at 570°C for 5 hours was prepared as Comparative Example 2.

[0197] Comparative Example 3

[0198] Sigma Aldrich's copper nanoparticle reagent (catalog code 794317) was prepared as Comparative Example 3.

[0199] Comparative Example 4

[0200] A powder obtained by calcining iron chloride at 500°C for 5 hours was prepared as Comparative Example 4.

[0201] Comparative Example 5

[0202] Mesoporous silica MCM-41 (catalog code 643645) from Sigma Aldrich was prepared as Comparative Example 5.

[0203] Comparative Example 6

[0204] No compound for the metal X dope was added. Aluminum chloride and zirconium oxychloride were added as compounds for the metal Y dope. Cobalt nitrate was added as a compound for the metal Z supply. The amount of each compound added was set to the following amounts per 1 mole of tetraethoxysilane.

[0205] Surfactant (Hexadecyltrimethylammonium chloride): 0.225 mol

[0206] Compound for Metal Y Dope (Aluminum Chloride): 0.0478 mol

[0207] Compound for metal Y dope (zirconium oxychloride): 0.035 mol

[0208] Compound for metal Z supply (cobalt nitrate): 0.0231 mol

[0209] Water: 125 moles

[0210] Sodium hydroxide: 0.282 mol

[0211] A deodorizing agent for Comparative Example 6 was prepared in the same manner as in Example 1 except for the other details.

[0212] Method for measuring specific surface area

[0213] Micromerics' Flosorb II2300 model was used, and measurements were taken at liquid nitrogen temperature using the single-point method.

[0214] Method for measuring the content of metal X and metal Y

[0215] About 50 mg of the deodorant according to the example or comparative example was accurately weighed and dissolved in 4 ml of hydrochloric acid, and then the concentration of each metal (Mn, Cu, Fe, Al, Co, and Zr) in the aqueous solution was measured using an ICP-OES manufactured by Thermo Scientific. It is believed that all metal components contained in the deodorant are dissolved in hydrochloric acid upon treatment with hydrochloric acid. Therefore, based on the measurement results, the content of each metal present in the deodorant was calculated as the metal content.

[0216] Cysteamine adsorption test

[0217] 0.5896 g of cysteamine was weighed into a 10 ml volumetric flask and mixed with ultrapure water to obtain Solution 1-1. The concentration of cysteamine in Solution 1-1 is 5.85 wt%, which is equivalent to the concentration of the undiluted perm solution.

[0218] 10 mg of the deodorant to be measured was weighed into a centrifuge tube. 0.9 ml of water was added to the tube and shaken well to create a homogeneous dispersion. 0.1 ml of Solution 1-1 was added to the dispersion and reacted by shaking well for 30 seconds. The cysteamine concentration before the reaction was 7.64 × 10⁻⁶. -2 The initial amount of cysteamine was 5.89 mg at mol / L. Centrifugation was performed for 90 seconds. The supernatant was rapidly extracted, and the absorbance of the reaction solution at 235 nm was measured.

[0219] From the measurement of the calibration curve, the cysteamine concentration is 7.5×10 -4 mol / L to 1.2×10 -4 It was confirmed that a proportional relationship exists between the absorbance at 235 nm and the cysteamine concentration within the mol / L range. Therefore, the reaction solution was appropriately diluted using an auto-pipette to fall within this concentration range, and the absorbance at 235 nm was measured. From the results, the residual concentration of cysteamine was calculated using Equation 1 below. In addition, the value of the adsorption rate was calculated using Equation 2 below.

[0220] (Equation 1) Residual concentration = Constant × Absorbance at 235 nm × Dilution factor

[0221] (Equation 2) Adsorption rate (%) = (Initial concentration - Remaining concentration) / Initial concentration × 100

[0222] Additionally, the capacity, etc., was calculated from the following formulas 3 to 5.

[0223] (Equation 3) Adsorption amount (mg) = Adsorption rate (%) × Initial amount of cysteamine (mg) / 100

[0224] (Equation 4) Amount of Metal X (mg) = Amount of Deodorizer (mg) × Metal × Amount of Metal (wt%) / 100

[0225] (Equation 5) Capacity (mg / Metal X mg) = Adsorbed amount (mg) / Amount of Metal X (mg)

[0226] In addition, the following was used as the absorbance measuring device.

[0227] Absorbance measuring device: Corona absorbance grating microplate reader SH-1000 (Korona Denki Co., Ltd.), Plate: UV Flat Bottom Microtite (registered trademark) Plates (Thermo), Measurement range: 200 to 600 nm, Response: 3

[0228] The measurement results are shown in Table 1 and Table 2.

[0229] As shown in Tables 1 and 2, the deodorizers according to Examples 1 to 7 had an improved cysteamine adsorption rate compared to the deodorizer according to Comparative Example 6. From this, it can be seen that the cysteamine adsorption performance is improved by incorporating metal X into porous silica.

[0230] In addition, the deodorizing agents according to Examples 1 to 8 had improved capacity for cysteamine adsorption compared to the deodorizing agents according to Comparative Examples 1 to 4, which did not use porous silica. From this, it can be seen that by incorporating metal X into porous silica, the deodorizing ability of metal X per unit mass is improved compared to when metal X is used as is. In other words, it can be seen that by incorporating metal X into porous silica, it is possible to achieve an equivalent or greater deodorizing ability using a small amount of metal X.

[0231] In addition, the deodorizers according to Examples 1 to 7 had a higher cysteamine adsorption rate compared to the deodorizer according to Example 8. From this, it can be seen that a higher specific surface area can obtain a higher cysteamine adsorption rate.

[0232] In addition, Examples 1 and 3 had higher cysteamine adsorption capacity (rate and capacity) compared to Example 6. From this, it was found that Mn and Cu are particularly preferred as metal X.

[0233]

[0234]

Claims

Claim 1 Porous silica used in liquid deodorizers, having a SiO4 framework, wherein at least one metal X selected from the group consisting of Mn, Cu, and Fe is incorporated and doped into the position of a Si element within the SiO4 framework in at least a first portion of the SiO4 framework, and having a metal different from said metal X, wherein the metal Y selected from the group consisting of Al and Zr is different from said metal X, and having a metal Y incorporated and doped into the position of a Si element within the SiO4 framework in at least a second portion of the SiO4 framework. Claim 2 In claim 1, porous silica having a metal Z selected from the group consisting of Co, Zn, Ag, and Ca, which is a metal different from the metal X. Claim 3 The porous silica of claim 1, having a structure with a chemical composition represented by the following Formula 1. (Formula 1) SiO2·aXO b / 2 ·cYO d / 2 ·eZO f / 2 (In Formula 1, X represents the metal X, Y represents the metal Y selected from the group consisting of Al and Zr, Z represents the metal Z selected from the group consisting of Co, Zn, Ag and Ca, a represents a number greater than 0 and less than or equal to 0.1, c and e represent numbers greater than or equal to 0 and less than or equal to 0.1, respectively, and b, d and f represent the valences of the metal X, the metal Y, and the metal Z, respectively.) Claim 4 In claim 1, porous silica having a specific surface area of ​​500 m² / g or more. Claim 5 A powder deodorant comprising porous silica as described in claim 1, which is a deodorant for permed hair. Claim 6 A liquid deodorizer comprising porous silica and a solvent as described in claim 1. Claim 7 In claim 6, a liquid deodorizer having a pH of 6 to 11. Claim 8 In paragraph 6, a liquid deodorant, which is a deodorant for permed hair. Claim 9 In paragraph 6, a liquid deodorizer containing sulfur for odors. Claim 10 In paragraph 6, a liquid deodorant containing, additionally, a fragrance or hair protective ingredient. Claim 11 In claim 6, a liquid deodorizer comprising water as the solvent. Claim 12 A liquid deodorizer according to claim 6, wherein the porous silica content is 0.001 to 50 mass%. Claim 13 A method for manufacturing a deodorizer, comprising the steps of: preparing porous silica having a SiO4 framework, wherein at least one metal X selected from the group consisting of Mn, Cu, and Fe, and a metal Y selected from the group consisting of Al and Zr are each incorporated into the positions of Si elements within the SiO4 framework in at least a first portion and a second portion of the SiO4 framework, respectively; and mixing the porous silica with a solvent. Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete

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