Metal-doped porous silica with surface modification.

Abstract

The present invention addresses the problem of providing a metal-doped porous silica that can, when being blended in an article such as cosmetics including permanent wave treating agents, sustain being stably dispersed therein. The metal-doped porous silica according to the present invention providing a solution to the problem is surface modified with a polymer including a vinylpyrrolidone unit. Specific examples of the polymer including the vinylpyrrolidone unit include: a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate; poly-vinylpyrrolidone; and the like.

Description

Technical Field

[0001] The present invention relates to a metal-doped porous silica that is surface-modified.

Background Art

[0002] It is well known that porous silica is used in various fields as an adsorbent, a humidity regulator, a catalyst carrier, and the like. In recent years, various attempts have been made to enhance the functionality of porous silica. As one of the research results, the present inventors have reported in Patent Document 1 that porous silica doped with a metal such as copper exhibits an excellent deodorizing effect against sulfur-containing odors.

[0003] The metal-doped porous silica reported by the present inventors in Patent Document 1 is expected to be used as a material for deodorizing the sulfur-containing odor remaining in hair after a perm treatment using a sulfur-containing substance such as cysteamine, L-cysteine, or thioglycolic acid as a reducing agent. However, in order to exert its effect without regret, it is important how to blend the metal-doped porous silica into a perm treatment agent and stably maintain its dispersion. In addition, it is necessary for the metal-doped porous silica to be stably maintained in dispersion when blended, which is the same for articles other than perm treatment agents.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Therefore, an object of the present invention is to provide a metal-doped porous silica that can be blended into an article such as a cosmetic exemplified by a perm treatment agent and stably maintained in dispersion. [Means for solving the problem]

[0006] In view of the above points, the present inventors conducted diligent studies and found that when metal-doped porous silica is added directly to an aqueous solution or aqueous dispersion of cationic polymers such as polyquaternium-10 (quaternary ammonium salt of hydroxyethylcellulose with glycidyltrimethylammonium chloride), polyquaternium-11 (quaternary ammonium salt of a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate with diethyl sulfate), and amodimethicone, which are commonly used as ingredients in cosmetics such as perm treatment agents, or to a nonionic polymer such as polyvinylpyrrolidone, the metal-doped porous silica is not stably dispersed and precipitates are formed. The inventors found that the formation of this precipitate can be suppressed by surface-modifying the metal-doped porous silica with a polymer containing vinylpyrrolidone units.

[0007] The present invention is based on the above findings. Deodorizer As described in claim 1, for use in aqueous solutions or aqueous dispersions of cationic polymers and / or nonionic polymers, which are surface-modified with a copolymer of vinylpyrrolidone units and units other than vinylpyrrolidone. , made of porous silica doped with metal . Furthermore, the claim described in claim 2 Deodorizer The following is the claim described in claim 1. Deodorizer In this configuration, the metal doped into the porous silica is at least one selected from the group consisting of copper, aluminum, zirconium, cobalt, manganese, and iron. Furthermore, the claim described in claim 3 Deodorizer The following is the claim described in claim 2. Deodorizer In this case, the metal doped into the porous silica is copper and / or aluminum. Also, the claim described in claim 4 Deodorizer The following is the claim described in claim 1. Deodorizer In this context, the copolymer of the vinylpyrrolidone unit and the units other than vinylpyrrolidone is a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. Furthermore, the claim 5 Deodorizer The following is the claim described in claim 1. Deodorizer In this case, an aqueous solution or aqueous dispersion of a cationic polymer and / or a nonionic polymer constitutes the cosmetic. Furthermore, the claim 6 Deodorizer The following is the claim described in claim 1. Deodorizer In this process, the cationic polymer is selected from polyquaternium-10, polyquaternium-11, and amodimethicone. Furthermore, the claim described in claim 7 Deodorizer The following is the claim described in claim 1. Deodorizer In this context, the nonionic polymer is polyvinylpyrrolidone. Furthermore, the slurry of the present invention is as described in claim 8, Deodorizer according to claim 1 The mixture is suspended in a dispersion medium. 。 [Effects of the Invention]

[0008] According to the present invention, it is possible to provide metal-doped porous silica that can be incorporated into articles such as cosmetics, exemplified by perming agents, and stably dispersed and maintained. [Modes for carrying out the invention]

[0009] The metal-doped porous silica of the present invention is surface-modified with a polymer containing vinylpyrrolidone units.

[0010] In the present invention, the metal-doped porous silica may be, for example, the one described by the present inventors in Japanese Patent Application Publication No. 2020-15640. Here, "metal-doped porous silica" means porous silica in which a metal is chemically bonded and incorporated into the inorganic network consisting of siloxane bonds that constitute the porous silica. Specifically, it is as follows.

[0011] Examples of metals that can be doped into porous silica include copper, aluminum, zirconium, cobalt, manganese, and iron. These may be used individually or in combination of two or more.

[0012] The content of the metal in the metal-doped porous silica (when two or more metals are used in combination, the total amount of each) is, for example, 0.01 to 10 wt%, preferably 0.1 to 5 wt%. When the content of the metal in the metal-doped porous silica is less than 0.01 wt%, there is a risk that a sufficient deodorizing effect cannot be obtained. On the other hand, porous silica doped with more than 10 wt% of the metal may be difficult to manufacture. When two or more metals are used in combination, the content ratio between the metals may be, for example, 0.1 to 2 times the content of one metal with respect to the content of the other metal.

[0013] Examples of the porous silica include mesoporous silica in which pores (mesopores) having a diameter of 2 to 50 nm are regularly arranged.

[0014] The specific surface area of the porous silica is, for example, 500 to 2000 m 2 / g, which is preferable in terms of maintaining durability.

[0015] The production of the metal-doped mesoporous silica can be carried out, for example, according to the following method known per se described in JP-A-2020-15640.

[0016] (Step 1) First, a surfactant and a raw material for doping the metal into the mesoporous silica are dissolved in a solvent and stirred, for example, at 30 to 200 °C for 0.5 to 10 hours to form micelles in the surfactant.

[0017] The amount of the surfactant dissolved in the solvent is, for example, 10 to 400 mmol / L, preferably 50 to 150 mmol / L. Alternatively, the amount of the surfactant dissolved in the solvent is, for example, 0.01 to 5.0 mol, preferably 0.05 to 1.0 mol, per 1 mol of the silica raw material added in Step 2 described later.

[0018] As the surfactant, cationic surfactants, anionic surfactants, and nonionic surfactants may be used, but cationic surfactants such as alkylammonium salts are preferred. Alkylammonium salts with an alkyl group having 8 or more carbon atoms are preferred, and those with an alkyl group having 12 to 18 carbon atoms are more preferred in light of ease of industrial availability. Specific 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, and ditetradecyldimethylammonium chloride. Surfactants may be used individually or in combination of two or more types.

[0019] The amount of raw materials to dissolve in the solvent for doping the metal into the mesoporous silica (the total amount of each raw material if two or more metals are used in combination) is, for example, 0.001 to 0.5 mol, preferably 0.01 to 0.1 mol, per 1 mol of silica raw material added in step 2 described later.

[0020] For doping mesoporous silica with metals, for example, metal nitrates, sulfates, chlorides, and oxychlorides can be used as raw materials. When doping with copper, it is preferable to use copper nitrate or copper chloride. When doping with aluminum, it is preferable to use aluminum chloride. When doping with zirconium, it is preferable to use zirconium oxychloride. When doping with cobalt, it is preferable to use cobalt nitrate. When doping with manganese, it is preferable to use manganese chloride. When doping with iron, it is preferable to use iron chloride. The raw materials for doping with metals may be used individually or in combination of two or more types.

[0021] For example, water can be used as the solvent. The solvent may be a mixed solvent of water and a water-soluble organic solvent, such as methanol, ethanol, diethylene glycol, or glycerin.

[0022] (Process 2) Next, the silica raw material is dissolved in the solution obtained in step 1, in which the surfactant forms micelles, for example at room temperature, and stirred until homogeneous, causing the silica raw material to accumulate on the surface of the surfactant micelles. The amount of silica raw material dissolved in the solution is, for example, 0.2 to 1.8 mol / L. Alternatively, when using water or a mixed solvent of water and a water-soluble organic solvent as the solvent, it is, for example, 0.001 to 0.05 mol per 1 mol of water.

[0023] The silica raw material is not particularly limited as long as it forms an inorganic network consisting of siloxane bonds that constitute mesoporous silica through dehydration condensation. Specific examples of silica raw materials include tetraalkoxysilanes such as tetraethoxysilane, tetramethoxysilane, and tetra-n-butoxysilane, and sodium silicate. Tetraalkoxysilane is preferred, and tetraethoxysilane is more preferred. The silica raw material may be used alone or in combination of two or more types.

[0024] (Step 3) Next, the silica raw material accumulated on the surface of the surfactant micelles is subjected to dehydration condensation to form an inorganic network consisting of siloxane bonds that constitute mesoporous silica, and metals are chemically bonded and incorporated into the inorganic network. Dehydration condensation of the silica raw material can be carried out, for example, by adding a basic aqueous solution to the system to raise the pH, and then stirring at room temperature for more than one hour. It is preferable to add the basic aqueous solution so that the pH becomes 8 to 14 immediately after addition, and more preferably so that the pH becomes 9 to 11. Specific examples of basic aqueous solutions include sodium hydroxide aqueous solution, sodium carbonate aqueous solution, and ammonia aqueous solution, but sodium hydroxide aqueous solution is preferred. The basic aqueous solution may be used alone or in combination of two or more types. In addition, dehydration condensation of the silica raw material can also be carried out by adding an acidic aqueous solution such as hydrochloric acid aqueous solution to the system to lower the pH, and then stirring.

[0025] (Step 4) Finally, the surfactant micelles obtained in step 3, which consist of siloxane bonds constituting the mesoporous silica and have an inorganic network in which metals are chemically bonded and incorporated, are collected by filtration as a precipitate. For example, they are dried at 30-70°C for 10-48 hours, and then calcined at 400-600°C for 1-10 hours to obtain mesoporous silica doped with the target metal. The metal-doped mesoporous silica thus obtained may be crushed in a mixer or mill as needed to obtain a desired particle size (for example, a median diameter of 0.01-100 μm is preferable as it facilitates stable dispersion and maintenance in the perm treatment agent).

[0026] Furthermore, the addition of raw materials for doping the mesoporous silica with metal to the system is not limited to dissolving them in a solvent together with a surfactant in step 1 above. It may also be dissolved in a solution in step 2 or step 3, as long as the formation of the inorganic network consisting of siloxane bonds constituting the mesoporous silica by dehydration condensation of the silica raw materials in step 3 is completed.

[0027] In the present invention, a polymer containing vinylpyrrolidone units is used to surface-modify metal-doped porous silica. The polymer containing vinylpyrrolidone units may be, for example, a copolymer of vinylpyrrolidone units and units other than vinylpyrrolidone. Specific examples include copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate, copolymers of vinylpyrrolidone and methylvinylimidazolinium chloride, copolymers of vinylpyrrolidone and dimethylaminopropyl methacrylate, copolymers of vinylpyrrolidone and quaternary imidazoline, and copolymers of vinylpyrrolidone, vinylcaprolactam, and methylvinylimidazolium methylsulfate. These copolymers are advantageous because their quaternary ammonium salts are already used as cosmetic ingredients under the cosmetic names polyquaternium-11, polyquaternium-16, polyquaternium-28, polyquaternium-44, and polyquaternium-46, respectively. Furthermore, copolymers of vinylpyrrolidone units and units other than vinylpyrrolidone include copolymers of vinylpyrrolidone and vinyl acetate, copolymers of vinylpyrrolidone and eicosene, copolymers of vinylpyrrolidone and hexadecene, and copolymers of vinylpyrrolidone and styrene. 、Copolymers of vinylpyrrolidone, vinylcaprolactam, and dimethylaminoethyl methacrylate can also be used. These are also convenient because they are already used as cosmetic ingredients. The polymer containing vinylpyrrolidone units may also be polyvinylpyrrolidone. Polyvinylpyrrolidone is also convenient because it is already used as a cosmetic ingredient. Considering the adhesion to metal-doped porous silica and the ease of surface modification, the suitable molecular weight of the polymer containing vinylpyrrolidone units is, for example, in the range of 5,000 to 5,000,000, depending on the type. If the polymer containing vinylpyrrolidone units is a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, its molecular weight is preferably in the range of 100,000 to 1,200,000, and if it is polyvinylpyrrolidone, its molecular weight is preferably in the range of 40,000 to 1,600,000. Furthermore, the suitable glass transition temperature (Tg) of the polymer containing vinylpyrrolidone units is, for example, in the range of 120 to 200°C, depending on the type.

[0028] The method for surface-modifying metal-doped porous silica with a polymer containing vinylpyrrolidone units is not particularly limited and can be carried out by mixing and stirring the metal-doped porous silica and the polymer containing vinylpyrrolidone units, adjusting the temperature as needed. A preferred method involves suspending the metal-doped porous silica in a dispersion medium to form a slurry, which is then placed in a processing container along with the polymer containing vinylpyrrolidone units and balls (media) used in a ball mill (the dispersion medium may also be added). The processing container containing these is then placed on a ball mill stand and rotated (the rotation speed is, for example, in the range of 15 to 500 rpm) to surface-treat the metal-doped porous silica. This method allows for the easy acquisition of metal-doped porous silica, surface-modified with a polymer containing vinylpyrrolidone units, in a form contained in a slurry that exhibits excellent dispersibility with perm treatment agents, such as cationic polymers like polyquaternium-10, polyquaternium-11, and amodimethicone, or nonionic polymers like polyvinylpyrrolidone. The ball milling time is, for example, 1 to 50 hours, preferably 6 to 30 hours. As the dispersion medium in the slurry, in which the metal-doped porous silica is suspended in a dispersion medium, or as a dispersion medium that may be further contained in the processing container, water can be used, for example. The water used as the dispersion medium may contain water-soluble organic solvents such as methanol, ethanol, diethylene glycol, and glycerin, but the water content is preferably 50 wt% or more. The pH of the dispersion medium is, for example, 5 to 11, preferably 6 to 9. If the pH of the dispersion medium falls below 5, the metal doped into the porous silica may dissolve, while if the pH of the dispersion medium exceeds 11, the porous silica may dissolve. Furthermore, if the pH of the dispersion medium is too acidic or too alkaline, it may adversely affect the properties of the perming agent.

[0029] The amounts of metal-doped porous silica and polymer containing vinylpyrrolidone units used are preferably such that the weight of the latter is 0.1 times or more the weight of the former. If the weight of the polymer containing vinylpyrrolidone units is too small compared to the weight of metal-doped porous silica, the effect of surface modification of the former with the latter may not be fully obtained, and the dispersibility with the perm treatment agent may decrease. By setting the weight of the polymer containing vinylpyrrolidone units to 0.5 times the weight of metal-doped porous silica, almost all or all of the latter can be attached to the former, and the effect of surface modification of the former with the latter can be fully obtained. If the weight of the polymer containing vinylpyrrolidone units exceeds 0.5 times the weight of metal-doped porous silica, the amount of free latter that does not attach to the former in the slurry will be large, but this is not a particular problem if the latter is already used as a cosmetic ingredient. However, it is preferable that the upper limit of the weight of the polymer containing vinylpyrrolidone units to the weight of metal-doped porous silica be 2 times. Slurries containing a large amount of polymers with free vinylpyrrolidone units are highly viscous and difficult to handle. Furthermore, adding such slurries to perming agents may affect the composition of the perming agent. It is preferable, for ease of handling, that the content of metal-doped porous silica, surface-modified with polymers containing vinylpyrrolidone units, in the slurry be, for example, 0.1 to 10 wt%. For the ball mill, it is preferable to use a number of balls (e.g., alumina balls or zirconia balls with a diameter of 1 to 5 mm) whose total weight is 1 to 5 times the total weight of the metal-doped porous silica, polymers containing vinylpyrrolidone units, and dispersion medium.

[0030] A perm treatment agent containing metal-doped porous silica, whose surface is modified with a polymer containing vinylpyrrolidone units, may be for straight perm treatment or for permanent wave treatment. Furthermore, a perm treatment agent containing metal-doped porous silica, whose surface is modified with a polymer containing vinylpyrrolidone units, may be a first agent containing a reducing agent such as cysteamine, L-cysteine, or thioglycolic acid; a second agent containing an oxidizing agent such as hydrogen peroxide or bromate; or an intermediate or post-treatment agent containing neither a reducing agent nor an oxidizing agent. The dosage form of the perm treatment agent containing metal-doped porous silica, whose surface is modified with a polymer containing vinylpyrrolidone units, may be, for example, liquid or cream. The amount of metal-doped porous silica, whose surface is modified with a polymer containing vinylpyrrolidone units, added to the perm treatment agent is preferably 0.01 to 5 wt%, and more preferably 0.02 to 0.5 wt%. If the amount of metal-doped porous silica, surface-modified with a polymer containing vinylpyrrolidone units, added to the perming agent is too small, the deodorizing effect on hair after perming by the metal-doped porous silica may decrease. On the other hand, if the amount of metal-doped porous silica, surface-modified with a polymer containing vinylpyrrolidone units, added to the perming agent is too large, it may lead to a decrease in the texture of the hair after perming, or make rinsing more difficult. The addition of metal-doped porous silica, surface-modified with a polymer containing vinylpyrrolidone units, to the perming agent can be done, for example, by adding a slurry of metal-doped porous silica, surface-modified with a polymer containing vinylpyrrolidone units, suspended in a dispersion medium, at any point in the manufacturing process of the perming agent.

[0031] In the above description, perming agents were used as an example of articles that can be formulated with metal-doped porous silica, which is surface-modified with a polymer containing vinylpyrrolidone units. However, articles that can be formulated with metal-doped porous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, may include various cosmetics, such as skincare cosmetics (cleansing cosmetics, skin conditioning cosmetics, protective cosmetics, whitening cosmetics, UV protection cosmetics, etc.), makeup cosmetics (base makeup cosmetics, point makeup cosmetics, etc.), haircare cosmetics (shampoo cosmetics, hair styling products, hair dyes, bleaching agents, etc.), bodycare cosmetics (body cleansing cosmetics, bath products, etc.), fragrance cosmetics, as well as quasi-drugs such as hair growth products, antiperspirants, and toothpastes, and any other articles in which metal-doped porous silica can exert a deodorizing effect.

[0032] Furthermore, porous silica doped with metals such as copper, which have antibacterial and antiviral properties, is expected to exhibit antibacterial and antiviral effects in addition to its deodorizing effect. Therefore, articles that can incorporate porous silica doped with metals such as copper, which is surface-modified with a polymer containing vinylpyrrolidone units, may include liquid and gel hand sanitizers, laundry detergents, fabric softeners, cleaners and cleaning agents (for toilet seats, bathrooms, windows, etc.), and waxes (for floors, walls, etc.). Moreover, porous silica doped with metals such as copper, which is surface-modified with a polymer containing vinylpyrrolidone units, can also be incorporated into articles such as textile products, nonwoven fabrics, leather products, building materials, wood, paints, adhesives, plastics, films, ceramics, paper, pulp, metalworking oils, water treatment agents, stationery, toys, containers, caps, dispensers, and spouts to impart antibacterial and antiviral properties. The method for incorporating porous silica, which is surface-modified with a polymer containing vinylpyrrolidone units and doped with a metal such as copper, into such articles may be the same as the known methods for incorporating inorganic antimicrobial agents and inorganic antiviral agents. [Examples]

[0033] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0034] Manufacturing Reference Example 1: Production of copper and aluminum-doped mesoporous silica Hexadecyltrimethylammonium chloride as a surfactant, copper chloride as a raw material for doping copper into mesoporous silica, and aluminum chloride as a raw material for doping aluminum into mesoporous silica were dissolved in water as a solvent, stirred at 100°C for 1 hour, cooled to room temperature, and then tetraethoxysilane as a silica raw material was further dissolved and stirred until homogeneous. Next, an aqueous sodium hydroxide solution as a basic aqueous solution was added to the reaction mixture so that the pH immediately after addition was 9, and the mixture was stirred at room temperature for 20 hours. The resulting precipitate was filtered and collected, dried at 50°C for 24 hours, and then calcined at 570°C for 5 hours to obtain the desired copper and aluminum-doped mesoporous silica as a slightly bluish-white powder.

[0035] The amounts used for hexadecyltrimethylammonium chloride as a surfactant, copper chloride as a raw material for doping copper into mesoporous silica, aluminum chloride as a raw material for doping aluminum into mesoporous silica, and water as a solvent were as follows, relative to 1 mol of tetraethoxysilane as the silica raw material. Hexadecyltrimethylammonium chloride: 0.225 mol Copper chloride: 0.0204 mol Aluminum chloride: 0.0482 mol Water: 125mol Furthermore, in order to prepare an aqueous sodium hydroxide solution as a basic aqueous solution, 0.195 moles of sodium hydroxide were used per mole of tetraethoxysilane, which was used as a silica raw material.

[0036] The copper and aluminum-doped mesoporous silica obtained by the above method has a specific surface area of ​​1100 m². 2The pore diameter was approximately 2.5 nm (measured by measuring the adsorption isotherm of nitrogen gas at liquid nitrogen temperature using a multi-point method with a BELSORP MAX II Microtrac-Bel and calculating it using BJH calculations). In addition, approximately 50 mg of copper and aluminum-doped mesoporous silica was accurately weighed out and dissolved in 4 mL of hydrochloric acid. The concentrations of copper and aluminum in the hydrochloric acid solution were then measured using an inductively coupled plasma atomic emission spectrometer (ICP-OES, Thermo Scientific). Based on the measurement results, the copper and aluminum content in the copper and aluminum-doped mesoporous silica was calculated to be 2.09 wt% for copper and 2.00 wt% for aluminum. The doping of copper and aluminum into the mesoporous silica was confirmed using an X-ray photoelectron spectrometer (K-Alpha Surface Analysis, Thermo Scientific) and a transmission electron microscope (JEM2010, JEOL).

[0037] Manufacturing Reference Example 2: Production of a slurry containing copper and aluminum-doped mesoporous silica In a 250 mL I-Boy PP wide-mouth bottle, 11 g of copper and aluminum-doped mesoporous silica produced in Manufacturing Reference Example 1, 99 g of water, and 220 g of 2 mmφ alumina balls were placed. The mixture was then treated at room temperature at 180 rpm on a ball mill stand for 8 hours. After removing the alumina balls, a slurry containing 10 wt% copper and aluminum-doped mesoporous silica with a median diameter of approximately 0.5 μm was obtained (median diameter was measured using a laser diffraction particle size distribution analyzer (SALD-3100, Shimadzu Corporation) (the same applies hereafter)).

[0038] Manufacturing Example 1: Preparation of a slurry (Part 1) obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium. In a 250 mL I-Boy PP wide-mouth bottle, 55 g of the slurry obtained in Manufacturing Reference Example 2, 11 g of HC Polymer 1N(M) from Osaka Organic Chemical Industry Co., Ltd. (containing 20 wt% polyquaternium-11 with a molecular weight of 500,000, Tg: 126°C), 44 g of water, and 220 g of 2 mmφ alumina balls were placed. The mixture was then treated at room temperature for 24 hours at a rotation speed of 90 rpm on a ball mill stand. After removing the alumina balls, a slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt%, and the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate was 2 wt%).

[0039] Manufacturing Example 2: Production of a slurry (part 2) obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium. In a 250 mL I-Boy PP wide-mouth bottle, 55 g of the slurry obtained in Manufacturing Reference Example 2, 22 g of a 10 wt% aqueous solution of polyvinylpyrrolidone K90 (polyvinylpyrrolidone with undisclosed molecular weight and Tg) from Fujifilm Wako Pure Chemical Industries, 33 g of water, and 220 g of 2 mmφ alumina balls were placed. The mixture was then treated at room temperature at 90 rpm on a ball mill stand for 24 hours. After removing the alumina balls, a slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with polyvinylpyrrolidone, was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt% and the content of polyvinylpyrrolidone was 2 wt%).

[0040] Manufacturing Example 3: Production of a slurry (Part 3) obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium. Except for using polyvinylpyrrolidone K30 (polyvinylpyrrolidone with undisclosed molecular weight and Tg) from Fujifilm Wako Pure Chemical Industries, Ltd., instead of polyvinylpyrrolidone K90 used in Production Example 2, a slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) surface-modified with polyvinylpyrrolidone was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt% and the content of polyvinylpyrrolidone was 2 wt%).

[0041] Manufacturing Example 4: Production of a slurry (Part 4) obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium. A slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with polyvinylpyrrolidone, was uniformly dispersed (copper and aluminum-doped mesoporous silica content: 5 wt% and polyvinylpyrrolidone content: 1 wt%), except that 11 g of a 10 wt% aqueous solution of polyvinylpyrrolidone K90 from Fujifilm Wako Pure Chemical Industries was placed in a 250 mL iBoy PP wide-mouth bottle, and 44 g of water was placed in the same manner as in Production Example 2.

[0042] Manufacturing Example 5: Preparation of a slurry (Part 5) obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium. A slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with polyvinylpyrrolidone, was uniformly dispersed (copper and aluminum-doped mesoporous silica content: 5 wt%, polyvinylpyrrolidone content: 4 wt%), except that 44 g of a 10 wt% aqueous solution of polyvinylpyrrolidone K90 from Fujifilm Wako Pure Chemical Industries was placed in a 250 mL iBoy PP wide-mouth bottle and 11 g of water, in the same manner as in Production Example 2.

[0043] Manufacturing Example 6: Preparation of a slurry (Part 6) obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium. Except for using HC Polymer 1NS (containing 20 wt% polyquaternium-11 with a molecular weight of 500,000, Tg: 126°C) from Osaka Organic Chemical Industry Co., Ltd. instead of HC Polymer 1N(M) from Osaka Organic Chemical Industry Co., Ltd. used in Production Example 1, a slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt%, and the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate was 2 wt%).

[0044] Manufacturing Example 7: Preparation of a slurry (Part 7) obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium. Except for using HC Polymer 2L (containing 20 wt% polyquaternium-11 with a molecular weight of 200,000, Tg: 126°C) from Osaka Organic Chemical Industry Co., Ltd. instead of HC Polymer 1N(M) from Osaka Organic Chemical Industry Co., Ltd. used in Production Example 1, a slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt%, and the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate was 2 wt%).

[0045] Manufacturing Example 8: Preparation of a slurry obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium (Part 8) Except for using HC Polymer 3M (containing 20 wt% polyquaternium-11 with a molecular weight of 300,000, Tg: 126°C) from Osaka Organic Chemical Industry Co., Ltd. instead of HC Polymer 1N(M) from Osaka Organic Chemical Industry Co., Ltd. used in Production Example 1, a slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt%, and the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate was 2 wt%).

[0046] Manufacturing Example 9: Preparation of a slurry (Part 9) obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium. Except for using HC Polymer 5 (containing 20 wt% polyquaternium-11 with a molecular weight of 150,000, Tg: 126°C) from Osaka Organic Chemical Industry Co., Ltd. instead of HC Polymer 1N(M) from Osaka Organic Chemical Industry Co., Ltd. used in Production Example 1, a slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt%, and the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate was 2 wt%).

[0047] Manufacturing Example 10: Preparation of a slurry (No. 10) obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium. Except for using HC Polymer 5W (containing 20 wt% polyquaternium-11 with a molecular weight of 300,000, Tg: 126°C) from Osaka Organic Chemical Industry Co., Ltd. instead of HC Polymer 1N(M) from Osaka Organic Chemical Industry Co., Ltd. used in Production Example 1, a slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt%, and the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate was 2 wt%).

[0048] Manufacturing Example 11: Preparation of a slurry obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium (Part 11) Except for using Rubiscol K90 (polyvinylpyrrolidone with a molecular weight of 1,200,000, Tg: undisclosed) from BASF Japan, instead of the polyvinylpyrrolidone K90 from Fujifilm Wako Pure Chemical Industries used in Production Example 2, a slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with polyvinylpyrrolidone, was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt% and the content of polyvinylpyrrolidone was 2 wt%).

[0049] Manufacturing Example 12: Preparation of a slurry (No. 12) obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium. Except for using Clejes K-90 (polyvinylpyrrolidone with a molecular weight of 1,200,000, Tg: undisclosed) from Daiichi Kogyo Seiyaku Co., Ltd. instead of polyvinylpyrrolidone K90 from Fujifilm Wako Pure Chemical Industries Co., Ltd., which was used in Production Example 2, a slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) surface-modified with polyvinylpyrrolidone was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt% and the content of polyvinylpyrrolidone was 2 wt%).

[0050] Manufacturing Example 13: Preparation of a slurry obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium (Part 13) Except for using Ashland's PVP K-90 (polyvinylpyrrolidone with a molecular weight of 900,000, Tg: undisclosed) instead of Fujifilm Wako Pure Chemical Industries' polyvinylpyrrolidone K90 used in Production Example 2, a slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) surface-modified with polyvinylpyrrolidone was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt% and the content of polyvinylpyrrolidone was 2 wt%).

[0051] Manufacturing Example 14: Preparation of a slurry obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium (Part 14) Except for using Ashland's Copolymer 845 (containing 20 wt% of a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate with a molecular weight of 1,000,000, Tg: 172°C) instead of Osaka Organic Chemical Industry's HC Polymer 1N(M) used in Production Example 1, a slurry was obtained in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt%, and the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate was 2 wt%).

[0052] Manufacturing Example 15: Preparation of a slurry obtained by suspending copper and aluminum-doped mesoporous silica in a dispersion medium. At room temperature, 50 g of water was added to 50 g of the slurry obtained in Manufacturing Reference Example 2 to obtain a slurry in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) was uniformly dispersed (content of copper and aluminum-doped mesoporous silica: 5 wt%).

[0053] Production Example 16: Preparation of a slurry obtained by suspending copper and aluminum-doped mesoporous silica, surface-modified with dodecylamine, in a dispersion medium. In a 250 mL I-Boy PP wide-mouth bottle, 50 g of the slurry obtained in Manufacturing Reference Example 2, 1 g of dodecylamine hydrochloride from Tokyo Chemical Industry Co., Ltd., and 49 g of water were placed and shaken well at room temperature to obtain a slurry in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with dodecylamine, was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt% and the content of dodecylamine was 1 wt%).

[0054] Production Example 17: Preparation of a slurry obtained by suspending copper and aluminum-doped mesoporous silica, which has been surface-modified with a mixture of a high molecular weight block copolymer and TWEEN(registered trademark)-20, in a dispersion medium. In a 250 mL iBoy PP wide-mouth bottle, 50 g of the slurry obtained in Manufacturing Reference Example 2, 0.25 g of DISPERBYK-190 (containing 40 wt% high molecular weight block copolymer) from BIC Chemie Japan, 0.25 g of TWEEN®-20 from Fujifilm Wako Pure Chemical Industries, and 49.5 g of water were added. The mixture was shaken well at room temperature to obtain a slurry in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm), surface-modified with a mixture of high molecular weight block copolymer and TWEEN®-20, was uniformly dispersed (the content of copper and aluminum-doped mesoporous silica was 5 wt%, the content of high molecular weight block copolymer was 0.10 wt%, and the content of TWEEN®-20 was 0.25 wt%).

[0055] Production Example 18: Preparation of a slurry obtained by suspending copper and aluminum-doped mesoporous silica, which is surface-modified with a silicone polymer (amodimethicone) whose terminals are modified with amino groups, in a dispersion medium. In this experiment, we attempted to obtain a slurry in which copper and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) surface-modified with amodimethicone was uniformly dispersed (copper and aluminum-doped mesoporous silica content: 5 wt%, amodimethicone content: 2 wt%), except that instead of the 10 wt% aqueous solution of polyvinylpyrrolidone K90 from Fujifilm Wako Pure Chemical Industries used in Production Example 2, we used a 10 wt% aqueous solution of amodimethicone prepared by diluting DOWSIL FZ-4671 (containing 31.7 wt% amodimethicone) from Dow Toray Industries, which was surface-modified with amodimethicone. However, a sticky, purple, foamy mucus adhered to the inner wall of the bottle and the surface of the alumina balls, and we were unable to obtain the slurry. The reason for this was thought to be that the multiple amino groups in amodimethicone caused crosslinking of copper and aluminum-doped mesoporous silica particles, leading to aggregation and agglomeration.

[0056] Table 1 summarizes the slurries produced in manufacturing examples 1-18.

[0057] [Table 1]

[0058] Reference Example 1: Analysis of copper and aluminum-doped mesoporous silica, surface-modified with polyvinylpyrrolidone, contained in the slurry produced in Production Examples 2, 4, and 5. Each of the slurries produced in Production Examples 2, 4, and 5 was filtered by suction using φ70 mm filter paper, and copper and aluminum-doped mesoporous silica, surface-modified with polyvinylpyrrolidone, was recovered onto the filter paper. The recovered copper and aluminum-doped mesoporous silica, surface-modified with polyvinylpyrrolidone, was dried at 100°C for about 1 hour without washing with water, cooled, and then approximately 8 mg was weighed out. The mass change was measured using a thermal analyzer (STA7220, Hitachi High-Tech Science Corporation) when the temperature was raised from 40°C to 600°C at a heating rate of 5°C / min and held at 600°C for 1 hour. Up to 100°C, it was assumed that the water contained in the copper and aluminum-doped mesoporous silica, which was surface-modified with polyvinylpyrrolidone, evaporated, and from 100°C onwards, the polyvinylpyrrolidone attached to the copper and aluminum-doped mesoporous silica disappeared. Using the formula ((AB) / A)×100(A: weight before heating - weight loss up to 100°C, B: weight after heating), the ratio of the weight of polyvinylpyrrolidone to the weight of the copper and aluminum-doped mesoporous silica, which was surface-modified with polyvinylpyrrolidone (measured value: %) was calculated. In addition, the ratio of the weight of polyvinylpyrrolidone to the total weight of the copper and aluminum-doped mesoporous silica and polyvinylpyrrolidone used to produce the slurry (calculated value: %) was calculated. The measured and calculated values ​​are shown in Table 2.

[0059] [Table 2]

[0060] As is clear from Table 2, in the slurries produced in Production Example 4 and Production Example 2, the measured and calculated proportions of polyvinylpyrrolidone were almost the same. This indicates that as long as the weight of polyvinylpyrrolidone relative to the weight of copper- and aluminum-doped mesoporous silica used to produce the slurry is at least 0.4 times, all of the polyvinylpyrrolidone adheres to the copper- and aluminum-doped mesoporous silica. In contrast, in the slurry produced in Production Example 5, the measured value was smaller than the calculated value. This indicates that not all of the polyvinylpyrrolidone used to produce the slurry adhered to the copper- and aluminum-doped mesoporous silica, and that free polyvinylpyrrolidone was included in the slurry.

[0061] Test Example 1: Evaluation of the dispersibility of polyquaternium-10 in aqueous solutions (Evaluation method) 0.5 mL each of the slurries prepared in Production Example 2 and 15, along with 1.5 mL of water, were added to 8 mL of a 1.25 wt% aqueous solution of polyquaternium-10 (manufactured by Sigma-Aldrich) in a glass container. The mixture was then stirred by shaking well for 10 seconds at room temperature and allowed to stand for 60 minutes. The appearance of the mixture was then visually inspected, and it was evaluated as follows: ○ if the copper and aluminum-doped mesoporous silica was stably dispersed and maintained, and × if a precipitate formed and the dispersion was not maintained.

[0062] (Evaluation results) The results are shown in Table 3. As is clear from Table 3, in the visual evaluation of the appearance of the mixture, the slurry produced in Production Example 2 was marked with a circle (○), while the slurry produced in Production Example 15 was marked with a cross (×). Therefore, it was found that when copper and aluminum-doped mesoporous silica is surface-modified with polyvinylpyrrolidone and then mixed into an aqueous solution of polyquaternium-10, the copper and aluminum-doped mesoporous silica is stably dispersed and maintained.

[0063] Test Example 2: Evaluation of the dispersibility of polyquaternium-11 in aqueous solutions (Evaluation method) 0.5 mL of each slurry prepared in Production Examples 1-17 and 1.5 mL of water were added to 8 mL of a 1.25 wt% aqueous solution of polyquaternium-11 (prepared using HC Polymer 1N(M) from Osaka Organic Chemical Industry Co., Ltd.) in a glass container. The mixture was stirred by shaking well for 10 seconds at room temperature, and then allowed to stand for 60 minutes. The appearance of the mixture was visually inspected, and it was evaluated as follows: ○ if the copper and aluminum-doped mesoporous silica was stably dispersed and maintained, and × if a precipitate formed and the dispersion was not maintained.

[0064] (Evaluation results) The results are shown in Table 3. As is clear from Table 3, in the visual evaluation of the appearance of the mixture, all samples using the slurries produced in Production Examples 1 to 14 were marked with a circle (○), while all samples using the slurries produced in Production Examples 15 to 17 were marked with a cross (×). Therefore, it was found that when copper and aluminum-doped mesoporous silica is surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate or polyvinylpyrrolidone and then mixed into an aqueous solution of polyquaternium-11, the copper and aluminum-doped mesoporous silica is stably dispersed and maintained.

[0065] Test Example 3: Evaluation of the dispersibility of amodimethicone in an aqueous dispersion. (Evaluation method) 0.5 mL of each slurry prepared in Production Examples 1-17 and 1.5 mL of water were added to 8 mL of a 1.25 wt% aqueous solution of amodimethicone (prepared using DOWSIL FZ-4671 from Dow-Toray) in a glass container. The mixture was stirred by shaking well for 10 seconds at room temperature, and then allowed to stand for 60 minutes. The appearance of the mixture was visually inspected, and it was evaluated as follows: ○ if the copper and aluminum-doped mesoporous silica was stably dispersed and maintained, and × if a precipitate formed and the dispersion was not maintained.

[0066] (Evaluation results) The results are shown in Table 3. As is clear from Table 3, in the visual evaluation of the appearance of the mixture, all samples using the slurries produced in Production Examples 1 to 14 were marked with a circle (○), while all samples using the slurries produced in Production Examples 15 to 17 were marked with a cross (×). Therefore, it was found that when copper and aluminum-doped mesoporous silica is surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate or polyvinylpyrrolidone and then blended into an aqueous dispersion of amodimethicone, the copper and aluminum-doped mesoporous silica is stably dispersed and maintained.

[0067] Test Example 4: Evaluation of the dispersibility of polyvinylpyrrolidone in aqueous solutions (Evaluation method) 0.5 mL each of the slurry prepared in Production Example 2 and 15, along with 1.5 mL of water, were placed in a glass container with 1.25 ml of polyvinylpyrrolidone. wt% After adding 8 mL of an aqueous solution (prepared using Rubiscol K90 from BASF Japan) and stirring well at room temperature for 10 seconds, the mixture was allowed to stand for 60 minutes. The appearance of the mixture was then visually inspected, and a circle (○) was used if the copper and aluminum-doped mesoporous silica was stably dispersed and maintained, while a cross (×) was used if a precipitate formed and the dispersion was not maintained.

[0068] (Evaluation results) The results are shown in Table 3. As is clear from Table 3, in the visual evaluation of the appearance of the mixture, the slurry produced in Production Example 2 was marked with a circle (○), while the slurry produced in Production Example 15 was marked with a cross (×). Therefore, it was found that when copper and aluminum-doped mesoporous silica is surface-modified with polyvinylpyrrolidone and then mixed into an aqueous solution of polyvinylpyrrolidone, the copper and aluminum-doped mesoporous silica is stably dispersed and maintained.

[0069] Test Example 5: Evaluation of adsorption activity for cysteamine (Evaluation method) Each of the slurries prepared in Production Examples 1-17 was placed in a centrifuge tube containing 0.1 mL of each slurry. 1.8 mL of water was added to the tubes and shaken well at room temperature to create a homogeneous dispersion. Then, 0.1 mL of a 5.86 wt% cysteamine aqueous solution was added, shaken well for 30 seconds, and then centrifuged for 90 seconds. The supernatant was then removed from the centrifuge tubes, and its absorbance at 235 nm was measured. The cysteamine concentration in the supernatant was determined from the calibration curve between the cysteamine aqueous solution concentration and absorbance. The adsorption rate (%) of each cysteamine in the slurries prepared in Production Examples 1-17 was calculated using the formula: ((0.293 wt% - cysteamine concentration in supernatant) / 0.293 wt%) × 100. The absorbance was measured using a Corona SH-1000 absorbance grating microplate reader from Corona Electric Co., Ltd.

[0070] (Evaluation results) The results are shown in Table 3. As is clear from Table 3, all of the slurries produced in Production Examples 1 to 17 had high adsorption rates to cysteamine, and no decrease in the adsorption rate to cysteamine was observed due to surface modification of the copper and aluminum-doped mesoporous silica with the surface modifier.

[0071] Reference Example 2: Zeta potential of slurries produced in manufacturing examples 1-17 The measurements were performed using Otsuka Electronics' zeta potential, particle size, and molecular weight measurement system (ELSZ-2000ZS). The results are shown in Table 3. Generally, the larger the absolute value of the zeta potential, the greater the electrostatic repulsion and the higher the dispersion stability. In fact, the slurry produced in Production Example 15 is a slurry in which copper and aluminum-doped mesoporous silica is uniformly dispersed, and its absolute value of zeta potential is 30 mV or higher. However, even in a slurry in which copper and aluminum-doped mesoporous silica is uniformly dispersed, when it is mixed with an aqueous solution or aqueous dispersion of cationic polymers such as polyquaternium-10, polyquaternium-11, and amodimethicone, charge cancellation occurs between the negatively charged copper and aluminum-doped mesoporous silica and the cationic polymer. As a result, crosslinking occurs through adsorption, and precipitation occurs due to aggregation and aggregation. In contrast, the slurries produced in Production Examples 1-14 all exhibited lower absolute zeta potentials compared to the slurry produced in Production Example 15. Despite the lower electrostatic repulsion, their high dispersion stability in the slurry is thought to be due to the high steric hindrance of the polymer containing vinylpyrrolidone units present on the surface of the copper- and aluminum-doped mesoporous silica. This repulsive force is believed to contribute to maintaining dispersion stability by inhibiting aggregation and agglomeration with the cationic polymer even after being mixed into aqueous solutions or dispersions of cationic polymers. The reason why the slurries produced in Production Examples 16 and 17 cannot maintain dispersion stability after being mixed into aqueous solutions or dispersions of cationic polymers is thought to be because the surface modifiers used have a chemical structure that does not produce the high steric hindrance repulsive force found in polymers containing vinylpyrrolidone units. The reason why precipitation occurs when the slurry produced in Production Example 15 is mixed with an aqueous solution of polyvinylpyrrolidone, a nonionic polymer, is not entirely clear, and is not thought to be due to the cancellation of charges as described above.However, the fact that no precipitate forms when the slurry produced in Production Example 2 is incorporated is thought to be due to the repulsive force caused by the high steric hindrance of polyvinylpyrrolidone present on the surface of the copper and aluminum-doped mesoporous silica.

[0072] [Table 3]

[0073] Application Example 1: Production of a perm treatment agent containing metal-doped porous silica, which is surface-modified with a polymer containing vinylpyrrolidone units. A slurry containing copper and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, obtained in Production Example 1, was added to a commercially available perm treatment agent (second agent) containing at least polyquaternium-11. By stirring thoroughly at room temperature, a perm treatment agent was produced in which copper and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was uniformly dispersed and contained at a content of 0.5 wt%.

[0074] Application Example 2: Production of a shampoo containing metal-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units. By adding a slurry containing copper and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone, obtained in Production Example 2, to a commercially available shampoo containing at least polyquaternium-10, and stirring well at room temperature, it was possible to produce a shampoo containing 0.5 wt% of copper and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone, in which the mesoporous silica was uniformly dispersed.

[0075] Application Example 3: Production of a hair treatment agent containing metal-doped porous silica, which is surface-modified with a polymer containing vinylpyrrolidone units. By adding a slurry containing copper and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone, obtained in Production Example 2, to a commercially available hair treatment agent containing at least amodimethicone, and stirring well at room temperature, it was possible to produce a hair treatment agent in which copper and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone was uniformly dispersed, with a content of 0.5 wt%.

[0076] Application Example 4: Production of a hair styling product containing metal-doped porous silica, which is surface-modified with a polymer containing vinylpyrrolidone units. By adding a slurry containing copper and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone, obtained in Production Example 2, to a commercially available hair styling agent containing at least polyvinylpyrrolidone and stirring well at room temperature, it was possible to produce a hair styling agent with a uniform dispersion of copper and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone, containing a content of 0.5 wt%.

[0077] Application Example 5: Manufacturing of a toilet seat cleaner containing metal-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units. By adding a slurry containing copper and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone, obtained in Production Example 2, to a commercially available toilet seat cleaner containing at least polyquaternium-55, and stirring well at room temperature, it was possible to produce a toilet seat cleaner in which copper and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone was uniformly dispersed, with a content of 0.5 wt%.

[0078] Application Example 6: Production of an alcohol hand gel containing metal-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units. By adding a slurry containing copper and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone, obtained in Production Example 13, to a commercially available alcohol hand gel containing at least carbomer, and stirring well at room temperature, it was possible to produce an alcohol hand gel with a uniform dispersion of copper and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone, containing a content of 0.5 wt%. [Industrial applicability]

[0079] The present invention has industrial applicability in that it can provide metal-doped porous silica that can be stably dispersed and maintained when incorporated into articles such as cosmetics, which are exemplified by perming agents.

Claims

1. A deodorant made of metal-doped porous silica for incorporation into aqueous solutions or aqueous dispersions of cationic polymers and / or nonionic polymers, which are surface-modified with copolymers of vinylpyrrolidone units and units other than vinylpyrrolidone.

2. The deodorant according to claim 1, wherein the metal doped into the porous silica is at least one selected from the group consisting of copper, aluminum, zirconium, cobalt, manganese, and iron.

3. The deodorant according to claim 2, wherein the metal doped into the porous silica is copper and / or aluminum.

4. The deodorant according to claim 1, wherein the copolymer of the vinylpyrrolidone unit and the unit other than vinylpyrrolidone is a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate.

5. The deodorant according to claim 1, wherein an aqueous solution or aqueous dispersion of a cationic polymer and / or a nonionic polymer constitutes the cosmetic.

6. The deodorant according to claim 1, wherein the cationic polymer is selected from polyquaternium-10, polyquaternium-11, and amodimethicone.

7. The deodorant according to claim 1, wherein the nonionic polymer is polyvinylpyrrolidone.

8. A slurry comprising the deodorant according to Claim 1 suspended in a dispersion medium.

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