Surface-modified metal-doped porous silica

Abstract

To provide a metal-doped porous silica which can be stably dispersed and maintained by being blended with an article such as a cosmetic exemplified by a permanent wave treatment agent.SOLUTION: The metal-doped porous silica of the present invention is surface-modified with a polymer containing a vinylpyrrolidone unit. Specific examples of the polymer containing a vinylpyrrolidone unit include a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, and polyvinylpyrrolidone.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a surface-modified porous silica doped with a metal. [Background technology]

[0002] It is well known that porous silica is used in various fields as an adsorbent, a humidity conditioner, a catalyst support, etc. In recent years, various attempts have been made to improve the functionality of porous silica, and the present inventors have reported in Patent Document 1 that, as one of their research results, 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 sulfur-containing odors remaining in hair after a perm treatment using a sulfur-containing substance such as cysteamine, L-cysteine, or thioglycolic acid as a reducing agent, but in order to fully utilize this effect, it is essential to know how to incorporate the metal-doped porous silica into a perm treatment agent and maintain it in a stable dispersion.The need for the metal-doped porous silica to be stably dispersed when incorporated also applies to products other than perm treatment agents. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-15640 Summary of the Invention [Problem 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 products such as cosmetics, exemplified by permanent wave treatment agents, and can be stably dispersed and maintained. [Means for solving the problem]

[0006] The present inventors have conducted extensive research in light of the above points and have found that when metal-doped porous silica is added directly to an aqueous solution or dispersion of a cationic polymer such as polyquaternium-10 (a quaternary ammonium salt of hydroxyethyl cellulose with glycidyltrimethylammonium chloride), polyquaternium-11 (a quaternary ammonium salt of a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate with diethyl sulfate), or amodimethicone, which are commonly used as ingredients in cosmetics such as perm treatment agents, or the nonionic polymer polyvinylpyrrolidone, the metal-doped porous silica does not remain stably dispersed and precipitates are formed, and 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 metal-doped porous silica of the present invention, which was made based on the above findings, is surface-modified with polyvinylpyrrolidone in an amount by weight more than 0.2 times the weight of the metal-doped porous silica, as described in claim 1, and is intended to be incorporated into an aqueous solution or dispersion of a cationic polymer and / or a nonionic polymer. The metal-doped porous silica described in claim 2 is the metal-doped porous silica described in 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. The metal-doped porous silica according to claim 3 is the metal-doped porous silica according to claim 2, wherein the metal doped into the porous silica is copper and / or aluminum. In addition, the metal-doped porous silica described in claim 4 is the metal-doped porous silica described in claim 1, in which an aqueous solution or aqueous dispersion of a cationic polymer and / or a nonionic polymer constitutes a cosmetic. The metal-doped porous silica according to claim 5 is the metal-doped porous silica according to claim 1, wherein the cationic polymer is selected from polyquaternium-10, polyquaternium-11, and amodimethicone. The metal-doped porous silica according to claim 6 is the metal-doped porous silica according to claim 1, wherein the nonionic polymer is polyvinylpyrrolidone. Furthermore, as described in claim 7, the slurry of the present invention is for blending metal-doped porous silica, which has been surface-modified with polyvinylpyrrolidone in a weight amount exceeding 0.2 times the weight of the metal-doped porous silica, with an aqueous solution or aqueous dispersion of a cationic polymer and / or a nonionic polymer, which is prepared by suspending metal-doped porous silica in a dispersion medium. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a metal-doped porous silica that can be blended into products such as cosmetics, exemplified by permanent wave treatment agents, and can be stably dispersed and maintained. DETAILED DESCRIPTION OF THE INVENTION

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

[0010] In the present invention, the metal-doped porous silica may be, for example, that described by the present inventors in JP 2020-15640 A. Here, "metal-doped porous silica" refers to 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, which can be used alone or in combination of two or more.

[0012] The metal content in the metal-doped porous silica (when two or more metals are used in combination, the total amount of each metal) is, for example, 0.01 to 10 wt%, preferably 0.1 to 5 wt%. If the metal content in the metal-doped porous silica is less than 0.01 wt%, a sufficient deodorizing effect may not be obtained, while porous silica doped with a metal in an amount exceeding 10 wt% may be difficult to manufacture. When two or more metals are used in combination, the ratio of the metal contents may be, for example, 0.1 to 2 times the content of one metal relative to the content of the other metal.

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

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

[0015] Metal-doped mesoporous silica can be produced according to the following method, which is known per se, for example, as described in JP-A-2020-15640.

[0016] (Process 1) First, a surfactant and raw materials for doping a metal into 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 surfactant dissolved in the solvent is, for example, 10 to 400 mmol / L, preferably 50 to 150 mmol / L, or, for example, 0.01 to 5.0 mol, preferably 0.05 to 1.0 mol, relative to 1 mol of the silica raw material added in Step 2 described below.

[0018] The surfactant may be a cationic surfactant, an anionic surfactant, or a nonionic surfactant, but is preferably a cationic surfactant such as an alkylammonium salt. The alkylammonium salt preferably has an alkyl group containing 8 or more carbon atoms, and from the perspective of industrial availability, an alkyl group containing 12 to 18 carbon atoms is more preferred. 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. The surfactant may be used alone or in combination of two or more.

[0019] The amount of raw material to be dissolved in the solvent for doping the metal into the mesoporous silica (the total amount of each raw material when 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 the silica raw material added in Step 2 described below.

[0020] As raw materials for doping mesoporous silica with metals, for example, metal nitrates, sulfates, chlorides, and oxychlorides can be used. 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 alone or in combination of two or more.

[0021] The solvent may be, for example, water, or 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 surfactant-forming micelle solution obtained in step 1, for example, at room temperature, and stirred until homogenous, allowing 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 water or a mixed solvent of water and a water-soluble organic solvent is used as the solvent, the amount 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 by 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 materials may be used alone or in combination of two or more.

[0024] (Step 3) Next, the silica raw material accumulated on the surface of the surfactant micelles is dehydrated and condensed to form an inorganic network consisting of siloxane bonds that constitute mesoporous silica, and a metal is incorporated into the inorganic network by chemical bonding. The dehydration and 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, followed by stirring at room temperature for at least one hour. The basic aqueous solution is preferably added so that the pH is 8 to 14 immediately after addition, and more preferably 9 to 11. Specific examples of basic aqueous solutions include aqueous sodium hydroxide, aqueous sodium carbonate, and aqueous ammonia, with aqueous sodium hydroxide being preferred. The basic aqueous solutions may be used alone or in combination of two or more. The dehydration and condensation of the silica raw material can also be carried out by adding an acidic aqueous solution such as an aqueous hydrochloric acid solution to the system to lower the pH, followed by stirring.

[0025] (Step 4) Finally, the surfactant micelles obtained in step 3, which form an inorganic network on the surface of the mesoporous silica consisting of siloxane bonds and incorporating metals by chemical bonding, are filtered and recovered as a precipitate, and then dried, for example, at 30 to 70°C for 10 to 48 hours, and then calcined at 400 to 600°C for 1 to 10 hours to obtain the desired metal-doped mesoporous silica. The metal-doped mesoporous silica thus obtained may be pulverized in a mixer or mill as needed to obtain the desired particle size (for example, a median diameter of 0.01 to 100 μm is preferred because it is easy to maintain stable dispersion in the perm treatment agent).

[0026] The addition of raw materials to the system for doping metal into mesoporous silica is not limited to the above-mentioned step 1 in which the raw materials are dissolved in a solvent together with a surfactant, but may be dissolved in a solution in step 2 or 3, as long as the silica raw materials are dissolved in the solution until the formation of an inorganic network consisting of siloxane bonds that constitutes mesoporous silica by dehydration condensation in step 3 is completed.

[0027] In the present invention, a polymer containing a vinylpyrrolidone unit is used to surface modify metal-doped porous silica. The polymer containing a vinylpyrrolidone unit may be, for example, a copolymer of a vinylpyrrolidone unit and a unit other than vinylpyrrolidone. Specific examples include a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, a copolymer of vinylpyrrolidone and methylvinylimidazolinium chloride, a copolymer of vinylpyrrolidone and dimethylaminopropylamide methacrylate, a copolymer of vinylpyrrolidone and quaternized imidazoline, and a copolymer of vinylpyrrolidone, vinylcaprolactam, and methylvinylimidazolium methyl sulfate. These copolymers are advantageous in that their quaternary ammonium salts are already used as cosmetic raw materials under the cosmetic names Polyquaternium-11, Polyquaternium-16, Polyquaternium-28, Polyquaternium-44, and Polyquaternium-46, respectively. In addition, copolymers of vinylpyrrolidone units and units other than vinylpyrrolidone can also be used, such as copolymers of vinylpyrrolidone and vinyl acetate, copolymers of vinylpyrrolidone and eicosene, copolymers of vinylpyrrolidone and hexadecene, copolymers of vinylpyrrolidone and styrene, and copolymers of vinylpyrrolidone, vinylcaprolactam, and dimethylaminoethyl methacrylate. These are also advantageous in that they are already used as cosmetic raw materials. The polymer containing the vinylpyrrolidone unit may be polyvinylpyrrolidone. Polyvinylpyrrolidone is also advantageous in that it is already used as a cosmetic raw material. In consideration of adhesion to metal-doped porous silica and ease of surface modification, the preferred molecular weight of the polymer containing the vinylpyrrolidone unit is, for example, in the range of 5,000 to 5,000,000, depending on the type of polymer. When the polymer containing a vinylpyrrolidone unit is a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, the molecular weight is preferably in the range of 100,000 to 1,200,000, and when it is polyvinylpyrrolidone, the molecular weight is preferably in the range of 40,000 to 1,600,000.The suitable glass transition temperature (Tg) of the polymer containing a vinylpyrrolidone unit is, for example, in the range of 120 to 200° C. depending on the type of polymer.

[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 necessary. However, a preferred method involves suspending metal-doped porous silica in a dispersion medium to form a slurry, which is placed in a treatment vessel together with the polymer containing vinylpyrrolidone units and balls (media) used in a ball mill (a dispersion medium may also be placed therein), and then placing the treatment vessel containing these on a ball mill stand and rotating it (the rotation speed is, for example, in the range of 15 to 500 rpm), thereby surface-treating the metal-doped porous silica. This method allows for the easy production of metal-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units in a slurry that exhibits excellent dispersibility in permanent treatment agents containing cationic polymers such as polyquaternium-10, polyquaternium-11, and amodimethicone, or nonionic polymers such as polyvinylpyrrolidone. The ball milling time is, for example, 1 to 50 hours, preferably 6 to 30 hours. Water can be used as the dispersion medium in the slurry containing the metal-doped porous silica suspended in the dispersion medium, or as a dispersion medium that may be further contained in the treatment vessel. The water used as the dispersion medium may contain a water-soluble organic solvent, such as methanol, ethanol, or a polyhydric alcohol such as diethylene glycol or 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 is below 5, the metal doped in the porous silica may dissolve, while if the pH of the dispersion medium is above 11, the porous silica may dissolve. Also, if the pH of the dispersion medium is too acidic or too alkaline, the properties of the perm treatment agent may be adversely affected.

[0029] The amounts of the metal-doped porous silica and the polymer containing vinylpyrrolidone units used are preferably at least 0.1 times the weight of the latter relative to the weight of the former. If the weight of the polymer containing vinylpyrrolidone units is too small relative to the weight of the metal-doped porous silica, the effect of surface-modifying the former with the latter may not be fully achieved, and dispersibility in perm treatment agents may be reduced. By limiting the weight of the polymer containing vinylpyrrolidone units to 0.5 times the weight of the metal-doped porous silica, almost all or all of the latter can be attached to the former, and the effect of surface-modifying the former with the latter can be fully achieved. If the weight of the polymer containing vinylpyrrolidone units relative to the weight of the metal-doped porous silica exceeds 0.5 times, the amount of free latter not attached to the former in the slurry will increase, 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 relative to the weight of the metal-doped porous silica be 2 times. Slurries containing a large amount of polymer containing free vinylpyrrolidone units are highly viscous and difficult to handle, and adding such slurries to permanent wave treatment agents may affect the composition of the permanent wave treatment agent. From the viewpoint of ease of handling the slurry, it is preferable that the content of metal-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units in the slurry be, for example, 0.1 to 10 wt %. It is preferable to use balls (e.g., alumina balls or zirconia balls with a diameter of 1 to 5 mm) in the ball mill in a number that is 1 to 5 times the total weight of the metal-doped porous silica, the polymer containing vinylpyrrolidone units, and the dispersion medium.

[0030] Perm treatment agents containing metal-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units may be used for straight perm treatment or permanent wave treatment. Furthermore, perm treatment agents containing metal-doped porous silica surface-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. Perm treatment agents containing metal-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units may be in the form of, for example, a liquid or a cream. The amount of metal-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units in the perm treatment agent is preferably 0.01 to 5 wt %, more preferably 0.02 to 0.5 wt %. If the amount of metal-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units blended into a perm treatment agent is too small, the deodorizing effect of the metal-doped porous silica on hair after perming may be reduced. On the other hand, if the amount of metal-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units blended into a perm treatment agent is too large, the texture of hair after perming may be reduced or rinsing may be troublesome. The blending of metal-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units into a perm treatment agent may be carried out, for example, by adding a slurry prepared by suspending metal-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units in a dispersion medium at any point in the process of producing the perm treatment agent.

[0031] In the above, a perm treatment agent has been described as an example of an article that can incorporate metal-doped porous silica that has been surface-modified with a polymer containing vinylpyrrolidone units. However, articles that can incorporate metal-doped porous silica that has been surface-modified with a polymer containing vinylpyrrolidone units include various cosmetics, such as skin care cosmetics (cleansing cosmetics, skin conditioning cosmetics, protective cosmetics, whitening cosmetics, UV protection cosmetics, etc.), makeup cosmetics (base makeup cosmetics, point makeup cosmetics, etc.), hair care cosmetics (hair washing cosmetics, hair styling agents, hair dyes, bleaches, etc.), body care cosmetics (body cleansing cosmetics, bath additives, etc.), and fragrance cosmetics, as well as quasi-drugs such as hair growth agents, antiperspirants, and dentifrices, and may be any article in which metal-doped porous silica can exert a deodorizing effect.

[0032] Furthermore, porous silica doped with a metal such as copper that has antibacterial or antiviral properties can be expected to exhibit antibacterial and antiviral effects in addition to deodorizing effects. Therefore, products that can incorporate porous silica doped with a metal such as copper and surface-modified with a polymer containing a vinylpyrrolidone unit include liquid or gel hand sanitizers, laundry detergents, laundry softeners, cleaners and detergents (for toilet seats, bathrooms, windows, etc.), and waxes (for floors, walls, etc.). Furthermore, porous silica doped with a metal such as copper and surface-modified with a polymer containing a vinylpyrrolidone unit can also be incorporated into textiles, nonwoven fabrics, leather products, building materials, wood, paints, adhesives, plastics, films, ceramics, paper, pulp, metalworking oils, water treatment agents, stationery, toys, containers, caps, spouts, and other products to impart antibacterial or antiviral properties. The method for blending the porous silica doped with a metal such as copper, which has been surface-modified with a polymer containing a vinylpyrrolidone unit, into such an article may be the same as the method for blending known inorganic antibacterial agents or inorganic antiviral agents. [Example]

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

[0034] Preparation Example 1: Preparation of copper and aluminum doped mesoporous silica Hexadecyltrimethylammonium chloride (surfactant), copper chloride (copper chloride), and aluminum chloride (aluminum chloride) were dissolved in water and stirred at 100°C for 1 hour. The mixture was then cooled to room temperature and tetraethoxysilane (silica precursor) was further dissolved and stirred until homogeneous. A basic aqueous solution of sodium hydroxide was then added to the reaction mixture, adjusting the pH to 9 immediately after addition, and the mixture was stirred at room temperature for 20 hours. The resulting precipitate was collected by filtration, 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 of 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 a silica raw material: Hexadecyltrimethylammonium chloride: 0.225 mol Copper chloride: 0.0204 mol Aluminum chloride: 0.0482 mol Water: 125mol To prepare a sodium hydroxide aqueous solution as a basic aqueous solution, 0.195 mol of sodium hydroxide was used per 1 mol of tetraethoxysilane 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 m 2The pore diameter was approximately 2.5 nm (calculated using the BJH calculation based on nitrogen gas adsorption isotherms measured at liquid nitrogen temperature using a multipoint method using a Microtrackbell BELSORP MAX II). Approximately 50 mg of copper- and aluminum-doped mesoporous silica was accurately weighed and dissolved in 4 mL of hydrochloric acid. The copper and aluminum concentrations in the hydrochloric acid solution were measured using an inductively coupled plasma optical emission spectrometer (Thermo Scientific ICP-OES). Based on the measurement results, the copper and aluminum contents in the copper- and aluminum-doped mesoporous silica were calculated to be 2.09 wt% and 2.00 wt%, respectively. The copper and aluminum doping of the mesoporous silica was confirmed using an X-ray photoelectron spectrometer (Thermo Scientific K-Alpha Surface Analysis) and a transmission electron microscope (JEOL JEM2010).

[0037] Preparation Example 2: Preparation of a slurry containing copper and aluminum doped mesoporous silica A 250 mL i-boy PP wide-mouth bottle was charged with 11 g of the copper- and aluminum-doped mesoporous silica produced in Reference Production Example 1, 99 g of water, and 220 g of 2 mm diameter alumina balls. The bottle was placed on a ball mill stand and treated at room temperature for 8 hours at a rotation speed of 180 rpm. The alumina balls were then removed, yielding a slurry containing 10 wt % copper- and aluminum-doped mesoporous silica with a median diameter of approximately 0.5 μm (the median diameter was measured using a laser diffraction particle size distribution analyzer (SALD-3100, manufactured by Shimadzu Corporation) (the same applies hereinafter)).

[0038] Production Example 1: Production of a slurry in which copper- and aluminum-doped mesoporous silica, surface-modified with a polymer containing vinylpyrrolidone units, is suspended in a dispersion medium (Part 1) A 250 mL i-boy PP wide-mouth bottle was charged with 55 g of the slurry obtained in Reference Manufacturing Example 2, 11 g of Osaka Organic Chemical Industry's HC Polymer 1N(M) (containing 20 wt% polyquaternium-11 with a molecular weight of 500,000, Tg: 126°C), 44 g of water, and 220 g of 2 mm diameter alumina balls. The bottle was placed on a ball mill stand and treated at room temperature for 24 hours at a rotation speed of 90 rpm. The alumina balls were then removed, yielding a slurry in which copper- and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) that had been 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] Production Example 2: Production of a slurry in which copper- and aluminum-doped mesoporous silica, surface-modified with a polymer containing vinylpyrrolidone units, is suspended in a dispersion medium (Part 2) A 250 mL i-boy PP wide-mouth bottle was charged with 55 g of the slurry obtained in Reference Manufacturing Example 2, 22 g of a 10 wt % aqueous solution of polyvinylpyrrolidone K90 (a polyvinylpyrrolidone whose molecular weight and Tg are not disclosed) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 33 g of water, and 220 g of 2 mm diameter alumina balls. The bottle was placed on a ball mill stand and treated at room temperature for 24 hours at a rotation speed of 90 rpm. The alumina balls were then removed, yielding a slurry in which copper- and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) that had been surface-modified with polyvinylpyrrolidone was uniformly dispersed (copper- and aluminum-doped mesoporous silica content: 5 wt %, polyvinylpyrrolidone content: 2 wt %).

[0040] Production Example 3: Production of a slurry in which copper- and aluminum-doped mesoporous silica, surface-modified with a polymer containing vinylpyrrolidone units, is suspended in a dispersion medium (Part 3) A slurry (content of copper- and aluminum-doped mesoporous silica: 5 wt %, content of polyvinylpyrrolidone: 2 wt %) was obtained in the same manner as in Production Example 2, except that polyvinylpyrrolidone K30 (polyvinylpyrrolidone whose molecular weight and Tg are not disclosed) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used instead of polyvinylpyrrolidone K90 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. used in Production Example 2. The slurry was surface-modified with polyvinylpyrrolidone and contained uniformly dispersed copper- and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm).

[0041] Production Example 4: Production of a slurry in which copper- and aluminum-doped mesoporous silica, surface-modified with a polymer containing vinylpyrrolidone units, is suspended in a dispersion medium (Part 4) A 250 mL i-boy PP wide-mouth bottle was charged with 11 g of a 10 wt % aqueous solution of polyvinylpyrrolidone K90 (manufactured by Fujifilm Wako Pure Chemical Industries) and 44 g of water, and the same procedure as in Production Example 2 was repeated to obtain a slurry (content of copper- and aluminum-doped mesoporous silica: 5 wt %, content of polyvinylpyrrolidone: 1 wt %) in which copper- and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) that had been surface-modified with polyvinylpyrrolidone was uniformly dispersed.

[0042] Production Example 5: Production of a slurry in which copper- and aluminum-doped mesoporous silica, surface-modified with a polymer containing vinylpyrrolidone units, is suspended in a dispersion medium (Part 5) A 250 mL i-boy PP wide-mouth bottle was charged with 44 g of a 10 wt % aqueous solution of polyvinylpyrrolidone K90 (manufactured by Fujifilm Wako Pure Chemical Industries) and 11 g of water, and the same procedure as in Production Example 2 was repeated to obtain a slurry (content of copper- and aluminum-doped mesoporous silica: 5 wt %, content of polyvinylpyrrolidone: 4 wt %) in which copper- and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) that had been surface-modified with polyvinylpyrrolidone was uniformly dispersed.

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

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

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

[0046] Production Example 9: Production of a slurry in which copper- and aluminum-doped mesoporous silica, surface-modified with a polymer containing vinylpyrrolidone units, is suspended in a dispersion medium (No. 9) A slurry (content of copper- and aluminum-doped mesoporous silica: 5 wt %, content of vinylpyrrolidone and dimethylaminoethyl methacrylate copolymer: 2 wt %) was obtained in the same manner as in Production Example 1, except that HC Polymer 5 (containing 20 wt % of polyquaternium-11 having a molecular weight of 150,000, Tg: 126°C) manufactured by Osaka Organic Chemical Industry Co., Ltd. was used instead of HC Polymer 1N(M) manufactured by Osaka Organic Chemical Industry Co., Ltd. used in Production Example 1. The slurry was uniformly dispersed with copper- and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) that had been surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate.

[0047] Production Example 10: Production of a slurry in which copper- and aluminum-doped mesoporous silica, surface-modified with a polymer containing vinylpyrrolidone units, is suspended in a dispersion medium (Part 10) A slurry (content of copper- and aluminum-doped mesoporous silica: 5 wt %, content of vinylpyrrolidone and dimethylaminoethyl methacrylate copolymer: 2 wt %) was obtained in the same manner as in Production Example 1, except that HC Polymer 5W (containing 20 wt % of polyquaternium-11 with a molecular weight of 300,000, Tg: 126°C) manufactured by Osaka Organic Chemical Industry Co., Ltd. was used instead of HC Polymer 1N (M) manufactured by Osaka Organic Chemical Industry Co., Ltd. used in Production Example 1. The slurry was uniformly dispersed with copper- and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) that had been surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate.

[0048] Production Example 11: Production of a slurry in which copper- and aluminum-doped mesoporous silica, surface-modified with a polymer containing vinylpyrrolidone units, is suspended in a dispersion medium (Part 11) A slurry (content of copper- and aluminum-doped mesoporous silica: 5 wt %, content of polyvinylpyrrolidone: 2 wt %) in which copper- and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) surface-modified with polyvinylpyrrolidone was uniformly dispersed was obtained in the same manner as in Production Example 2, except that Luviscol K90 (polyvinylpyrrolidone having a molecular weight of 1,200,000, Tg: undisclosed) manufactured by BASF Japan was used instead of polyvinylpyrrolidone K90 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0049] Production Example 12: Production of a slurry in which copper- and aluminum-doped mesoporous silica, surface-modified with a polymer containing vinylpyrrolidone units, is suspended in a dispersion medium (Part 12) A slurry (content of copper- and aluminum-doped mesoporous silica: 5 wt %, content of polyvinylpyrrolidone: 2 wt %) was obtained in the same manner as in Production Example 2, except that Cleansius K-90 (polyvinylpyrrolidone with a molecular weight of 1,200,000, Tg: undisclosed) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was used instead of the polyvinylpyrrolidone K90 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0050] Production Example 13: Production of a slurry in which copper- and aluminum-doped mesoporous silica, surface-modified with a polymer containing vinylpyrrolidone units, is suspended in a dispersion medium (Part 13) A slurry (content of copper- and aluminum-doped mesoporous silica: 5 wt %, content of polyvinylpyrrolidone: 2 wt %) was obtained in the same manner as in Production Example 2, except that PVP K-90 (polyvinylpyrrolidone with a molecular weight of 900,000, Tg: undisclosed) manufactured by Ashland Chemical Industries was used instead of polyvinylpyrrolidone K90 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0051] Production Example 14: Production of a slurry in which copper- and aluminum-doped mesoporous silica, surface-modified with a polymer containing vinylpyrrolidone units, is suspended in a dispersion medium (Part 14) A slurry (content of copper- and aluminum-doped mesoporous silica: 5 wt %, content of vinylpyrrolidone-dimethylaminoethyl methacrylate copolymer: 2 wt %) was obtained in the same manner as in Production Example 1, except that 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) was used instead of Osaka Organic Chemical Industry's HC Polymer 1N (M) used in Production Example 1. The slurry was surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate and contained uniformly dispersed copper- and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm).

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

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

[0054] Preparation Example 17: Preparation of a slurry in which copper and aluminum doped mesoporous silica, surface-modified with a mixture of a high molecular weight block copolymer and TWEEN®-20, is suspended in a dispersion medium 50 g of the slurry obtained in Reference Manufacturing Example 2, 0.25 g of DISPERBYK-190 (containing 40 wt% of a high molecular weight block copolymer) manufactured by BYK Japan, 0.25 g of TWEEN®-20 manufactured by Fujifilm Wako Pure Chemical Industries, and 49.5 g of water were placed in a 250 mL i-boy PP wide-mouth bottle, and the bottle was vigorously shaken and stirred 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 the high molecular weight block copolymer and TWEEN®-20 was uniformly dispersed (copper- and aluminum-doped mesoporous silica content: 5 wt%, high molecular weight block copolymer content: 0.10 wt%, TWEEN®-20 content: 0.25 wt%).

[0055] Production Example 18: Production of a slurry obtained by suspending copper- and aluminum-doped mesoporous silica, surface-modified with a silicone polymer (amodimethicone) whose terminals are modified with amino groups, in a dispersion medium An attempt was made to obtain a slurry (copper- and aluminum-doped mesoporous silica content: 5 wt%, amodimethicone content: 2 wt%) in which copper- and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) surface-modified with amodimethicone was uniformly dispersed, in the same manner as in Production Example 2, except that a 10 wt% aqueous solution of amodimethicone, prepared by diluting DOWSIL FZ-4671 (containing 31.7 wt% amodimethicone) with water, was used instead of the 10 wt% aqueous solution of polyvinylpyrrolidone K90 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. used in Production Example 2. However, a purple, sticky, foamy, viscous liquid stuck to the inner wall of the bottle and the surface of the alumina balls, and the slurry was not obtained. This was thought to be due to the multiple amino groups in amodimethicone causing cross-linking of the copper and aluminum doped mesoporous silica particles, which then aggregated and formed agglomerates.

[0056] The slurries produced in Production Examples 1 to 18 are summarized in Table 1.

[0057] [Table 1]

[0058] Reference Example 1: Analysis of copper and aluminum doped mesoporous silica surface-modified with polyvinylpyrrolidone contained in the slurries produced in Production Examples 2, 4, and 5 Each of the slurries produced in Production Examples 2, 4, and 5 was suction-filtered through a 70 mm diameter filter, and the copper- and aluminum-doped mesoporous silica, surface-modified with polyvinylpyrrolidone, was collected on the filter. The collected polyvinylpyrrolidone-surface-modified mesoporous silica, doped with copper and aluminum, was dried at 100°C for approximately 1 hour without being washed with water. After cooling, approximately 8 mg of the mesoporous silica was weighed out and heated from 40°C to 600°C at a rate of 5°C / min. The mass change during the 1-hour hold at 600°C was measured using a thermal analyzer (STA7220, manufactured by Hitachi High-Tech Science Corporation). The water contained in the copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone evaporates up to 100°C, and the polyvinylpyrrolidone attached to the copper- and aluminum-doped mesoporous silica disappears above 100°C. The weight ratio of polyvinylpyrrolidone to the weight of the copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone (measured value: %) was calculated using the formula ((AB) / A) × 100 (A: weight before heating - weight lost up to 100°C, B: weight after heating). The weight ratio of polyvinylpyrrolidone to the total weight of the copper- and aluminum-doped mesoporous silica and polyvinylpyrrolidone used to prepare the slurry (calculated value: %) was also calculated. The measured and calculated values ​​are shown in Table 2.

[0059] [Table 2]

[0060] As is clear from Table 2, the measured and calculated proportions of polyvinylpyrrolidone are almost the same in the slurries produced in Production Examples 4 and 2, indicating that all of the polyvinylpyrrolidone adheres to the copper- and aluminum-doped mesoporous silica up to a weight ratio of at least 0.4 times the weight of the copper- and aluminum-doped mesoporous silica used to produce the slurry. In contrast, the measured value is smaller than the calculated value in the slurry produced in Production Example 5, indicating that not all of the polyvinylpyrrolidone used to produce the slurry adheres to the copper- and aluminum-doped mesoporous silica, and that free polyvinylpyrrolidone is contained in the slurry.

[0061] Test Example 1: Evaluation of dispersibility of Polyquaternium-10 in aqueous solution (Evaluation method) 0.5 mL of each of the slurries produced in Production Examples 2 and 15 and 1.5 mL of water were added to 8 mL of a 1.25 wt % aqueous solution of Polyquaternium-10 (Sigma-Aldrich) in a glass container, and the mixture was stirred by shaking vigorously for 10 seconds at room temperature. After leaving the mixture to stand for 60 minutes, the appearance of the mixture was visually inspected and evaluated with an O if the copper- and aluminum-doped mesoporous silica was stably dispersed and maintained, or an X if the dispersion was not maintained and a precipitate had formed.

[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 mixed liquid, the result was ○ when the slurry produced in Production Example 2 was used, and × when the slurry produced in Production Example 15 was used. Therefore, it was found that when mesoporous silica doped with copper and aluminum is surface-modified with polyvinylpyrrolidone and blended 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 dispersibility of Polyquaternium-11 in aqueous solution (Evaluation method) 0.5 mL of each of the slurries produced in Production Examples 1 to 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.) placed in a glass container, and the mixture was stirred by shaking vigorously for 10 seconds at room temperature, and then allowed to stand for 60 minutes.The appearance of the mixture was visually inspected, and evaluated with ○ if the copper- and aluminum-doped mesoporous silica was stably dispersed and maintained, or × if it was not dispersed and a precipitate had formed.

[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 mixed liquid, all of the cases where the slurries produced in Production Examples 1 to 14 were used were rated as ○, and all of the cases where the slurries produced in Production Examples 15 to 17 were used were rated as ×. Therefore, it was found that when mesoporous silica doped with copper and aluminum is surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate or polyvinylpyrrolidone and blended 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 dispersibility of amodimethicone in aqueous dispersion (Evaluation method) 0.5 mL of each of the slurries produced in Production Examples 1 to 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 Industries) placed in a glass container, and the mixture was stirred by shaking vigorously for 10 seconds at room temperature and then allowed to stand for 60 minutes. The appearance of the mixture was visually inspected and evaluated as follows: ◯ if the copper- and aluminum-doped mesoporous silica was stably dispersed and maintained; × if the dispersion was not maintained and a precipitate had formed.

[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 mixed liquid, all the cases where the slurries produced in Production Examples 1 to 14 were used were rated as ○, and all the cases where the slurries produced in Production Examples 15 to 17 were used were rated as ×. Therefore, it was found that when mesoporous silica doped with copper and aluminum is surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate or polyvinylpyrrolidone and blended with an aqueous dispersion of amodimethicone, the copper and aluminum-doped mesoporous silica is stably maintained in dispersion.

[0067] Test Example 4: Evaluation of dispersibility of polyvinylpyrrolidone in aqueous solution (Evaluation method) 0.5 mL of each of the slurries produced in Production Examples 2 and 15 and 1.5 mL of water were added to 8 mL of a 1.25 wt % aqueous solution of polyvinylpyrrolidone (prepared using Luviscol K90 from BASF Japan) placed in a glass container, and the mixture was stirred by shaking vigorously for 10 seconds at room temperature and then allowed to stand for 60 minutes. The appearance of the mixture was then visually inspected and evaluated with an O if the copper- and aluminum-doped mesoporous silica was stably dispersed and maintained, or an X if it was not dispersed and a precipitate had formed.

[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 mixed liquid, the result was ○ when the slurry produced in Production Example 2 was used, and × when the slurry produced in Production Example 15 was used. Therefore, it was found that when mesoporous silica doped with copper and aluminum is surface-modified with polyvinylpyrrolidone and blended 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 effect on cysteamine (Evaluation method) To centrifuge tubes containing 0.1 mL of each of the slurries produced in Production Examples 1 to 17, 1.8 mL of water was added and the tubes were shaken vigorously at room temperature to form a uniform dispersion. Then, 0.1 mL of a 5.86 wt% aqueous cysteamine solution was added, and the tubes were shaken vigorously for 30 seconds, followed by centrifugation for 90 seconds. The supernatant was then removed from the centrifuge tube, and its absorbance at 235 nm was measured. The cysteamine concentration of the supernatant was determined from a calibration curve of the cysteamine aqueous solution concentration and absorbance. The adsorption rate (%) of each of the slurries produced in Production Examples 1 to 17 to cysteamine was calculated using the formula ((0.293 wt% - cysteamine concentration of the supernatant) / 0.293 wt%) × 100. Absorbance measurements were performed using a Corona Electric Co., Ltd. Corona absorbance grating microplate reader SH-1000.

[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 for cysteamine, and no decrease in the adsorption rate for cysteamine was observed due to the surface modification of the copper- and aluminum-doped mesoporous silica with a surface modifier.

[0071] Reference Example 2: Zeta potential of slurries produced in Production Examples 1 to 17 The measurements were performed using an Otsuka Electronics Zeta Potential, Particle Size, and Molecular Weight Measurement System (ELSZ-2000ZS). The results are shown in Table 3. Generally, the greater the absolute value of the zeta potential, the greater the electrostatic repulsion and the higher the dispersion stability. In fact, the slurry produced in Preparation Example 15, in which copper- and aluminum-doped mesoporous silica was uniformly dispersed, had an absolute zeta potential of 30 mV or greater. However, even when this slurry containing uniformly dispersed copper- and aluminum-doped mesoporous silica was blended with an aqueous solution or dispersion of a cationic polymer such as polyquaternium-10, polyquaternium-11, or amodimethicone, the negatively charged copper- and aluminum-doped mesoporous silica and the cationic polymer cancel each other out, resulting in cross-linking due to adsorption, aggregation, and agglomeration, resulting in precipitation. In contrast, the slurries produced in Production Examples 1 to 14 all had smaller absolute zeta potentials than the slurry produced in Production Example 15. Despite the small electrostatic repulsion, the slurries exhibited high dispersion stability in the slurries. This is thought to be due to the repulsive force resulting from the high steric hindrance of the vinylpyrrolidone unit-containing polymer present on the surface of the copper- and aluminum-doped mesoporous silica. This repulsive force contributes to maintaining dispersion stability by inhibiting aggregation and agglomeration with the cationic polymer even after blending into an aqueous solution or dispersion of the cationic polymer. The slurries produced in Production Examples 16 and 17 were unable to maintain dispersion stability after blending into an aqueous solution or dispersion of the cationic polymer because the surface modifiers used had chemical structures that did not produce repulsive forces due to high steric hindrance, such as those of the vinylpyrrolidone unit-containing polymer. When the slurry produced in Production Example 15 is mixed with an aqueous solution of polyvinylpyrrolidone, a nonionic polymer, precipitation occurs. The reason for this is not necessarily clear, and is not thought to be due to the cancellation of charges as described above.However, the fact that no precipitation occurs when the slurry produced in Production Example 2 is blended 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 permanent treatment agent containing metal-doped porous silica whose surface has been modified with a polymer containing vinylpyrrolidone units The 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 permanent wave treatment agent (second agent) containing at least polyquaternium-11, and the mixture was stirred thoroughly at room temperature to produce a permanent wave treatment agent containing 0.5 wt% of uniformly dispersed copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate.

[0074] Application Example 2: Production of shampoo containing metal-doped porous silica whose surface has been modified with a polymer containing vinylpyrrolidone units The slurry containing copper- and aluminum-doped mesoporous silica that had been surface-modified with polyvinylpyrrolidone, obtained in Production Example 2, was added to a commercially available shampoo containing at least polyquaternium-10, and the mixture was stirred thoroughly at room temperature to produce a shampoo containing 0.5 wt% of uniformly dispersed copper- and aluminum-doped mesoporous silica that had been surface-modified with polyvinylpyrrolidone.

[0075] Application Example 3: Production of a hair treatment agent containing metal-doped porous silica whose surface has been modified with a polymer containing a vinylpyrrolidone unit The slurry containing mesoporous silica doped with copper and aluminum and surface-modified with polyvinylpyrrolidone obtained in Production Example 2 was added to a commercially available hair treatment agent containing at least amodimethicone, and the mixture was stirred thoroughly at room temperature to produce a hair treatment agent containing 0.5 wt% of uniformly dispersed mesoporous silica doped with copper and aluminum and surface-modified with polyvinylpyrrolidone.

[0076] Application Example 4: Production of a hair styling agent containing metal-doped porous silica whose surface has been modified with a polymer containing a vinylpyrrolidone unit The slurry containing mesoporous silica doped with copper and aluminum and surface-modified with polyvinylpyrrolidone obtained in Production Example 2 was added to a commercially available hair styling agent containing at least polyvinylpyrrolidone, and the mixture was thoroughly stirred at room temperature, thereby producing a hair styling agent containing 0.5 wt% of mesoporous silica doped with copper and aluminum and surface-modified with polyvinylpyrrolidone, in which the mesoporous silica was uniformly dispersed.

[0077] Application Example 5: Production of a toilet seat cleaner containing metal-doped porous silica whose surface has been modified with a polymer containing vinylpyrrolidone units The slurry containing copper- and aluminum-doped mesoporous silica that had been surface-modified with polyvinylpyrrolidone, obtained in Production Example 2, was added to a commercially available toilet seat cleaner containing at least polyquaternium-55, and the mixture was stirred thoroughly at room temperature to produce a toilet seat cleaner containing 0.5 wt% of uniformly dispersed copper- and aluminum-doped mesoporous silica that had been surface-modified with polyvinylpyrrolidone.

[0078] Application Example 6: Production of alcohol hand gel containing metal-doped porous silica whose surface has been modified with a polymer containing vinylpyrrolidone units The slurry containing copper- and aluminum-doped mesoporous silica that had been surface-modified with polyvinylpyrrolidone, obtained in Production Example 13, was added to a commercially available alcohol hand gel containing at least carbomer, and the mixture was stirred thoroughly at room temperature to produce an alcohol hand gel containing 0.5 wt% of uniformly dispersed copper- and aluminum-doped mesoporous silica that had been surface-modified with polyvinylpyrrolidone. [Industrial Applicability]

[0079] The present invention has industrial applicability in that it can provide metal-doped porous silica that can be blended into products such as cosmetics, exemplified by perm treatment agents, and maintained in a stable dispersion state.

Claims

1. The metal-doped porous silica is surface-modified with polyvinylpyrrolidone in an amount by weight exceeding 0.2 times the weight of the metal-doped porous silica, and is intended to be incorporated into an aqueous solution or dispersion of a cationic polymer and / or a nonionic polymer.

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

4. 2. The metal-doped porous silica according to claim 1, wherein the aqueous solution or dispersion of the cationic polymer and / or nonionic polymer constitutes a cosmetic product.

5. 2. The metal-doped porous silica according to claim 1, wherein the cationic polymer is selected from the group consisting of polyquaternium-10, polyquaternium-11, and amodimethicone.

6. 2. The metal-doped porous silica according to claim 1, wherein the nonionic polymer is polyvinylpyrrolidone.

7. The slurry is prepared by suspending metal-doped porous silica, the surface of which is modified with polyvinylpyrrolidone in an amount by weight exceeding 0.2 times the weight of the metal-doped porous silica, in a dispersion medium, for blending with an aqueous solution or aqueous dispersion of a cationic polymer and / or a nonionic polymer.

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