SURFACE-MODIFIED AND METAL-DOPED POROUS SILICA

Abstract

An object of the present invention is to provide a metal-doped porous silica that can be blended into an article, for example, a cosmetic product such as a perm treatment agent, and kept stably dispersed therein. The metal-doped porous silica of the present invention as a means for resolution is surface-modified with a vinylpyrrolidone unit-containing polymer. As specific examples of vinylpyrrolidone unit-containing polymers, a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, polyvinylpyrrolidone, and the like can be mentioned.

Claims

1. A metal-doped porous silica surface-modified with a vinylpyrrolidone unit-containing polymer.

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

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

4. The metal-doped porous silica according to claim 1, wherein the vinylpyrrolidone unit-containing polymer is a copolymer of a vinylpyrrolidone unit and a non-vinylpyrrolidone unit.

5. The metal-doped porous silica according to claim 4, wherein the copolymer of a vinylpyrrolidone unit and a non-vinylpyrrolidone unit is a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate.

6. The metal-doped porous silica according to claim 1, wherein the vinylpyrrolidone unit-containing polymer is polyvinylpyrrolidone.

7. A method for producing a metal-doped porous silica surface-modified with a vinylpyrrolidone unit-containing polymer, comprising a step in which a slurry of a metal-doped porous silica suspended in a dispersion medium is housed in a treatment container together with a vinylpyrrolidone unit-containing polymer and balls for use in ball milling (media) (a dispersion medium may further be housed), and the treatment container housing them is put on a ball mill stand and rotated, thereby surface-treating the metal-doped porous silica.

8. A slurry comprising a metal-doped porous silica surface-modified with a vinylpyrrolidone unit-containing polymer suspended in a dispersion medium.

9. Use of the metal-doped porous silica surface-modified with a vinylpyrrolidone unit-containing polymer according to claim 1 for deodorizing an article by blending into an article containing at least one member selected from the group consisting of polyquaternium-10, polyquaternium-11, amodimethicone, and polyvinylpyrrolidone.

Description

EXAMPLES

[0041] Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention should not be construed as being limited to the following descriptions.

Production Reference Example 1: Production of Copper- and Aluminum-Doped Mesoporous Silica

[0042] Hexadecyltrimethylammonium chloride as a surfactant, copper chloride as a raw material for doping copper in a mesoporous silica, and aluminum chloride as a raw material for doping aluminum in a mesoporous silica were dissolved in water as a solvent, stirred at 100 C. for 1 hour, and then cooled to room temperature. After that, tetraethoxysilane as a silica raw material was further dissolved and stirred until uniform. Next, an aqueous sodium hydroxide solution as a basic aqueous solution was added to the reaction liquid such that the pH immediately after the addition was 9, and stirred at room temperature for 20 hours. The formed precipitates were collected by filtration, dried at 50 C. for 24 hours, and then calcined at 570 C. for 5 hours, thereby giving the intended copper- and aluminum-doped mesoporous silica as a slightly bluish white powder.

[0043] Incidentally, the amounts of hexadecyltrimethylammonium chloride as a surfactant, copper chloride as a raw material for doping copper in a mesoporous silica, aluminum chloride as a raw material for doping aluminum in a mesoporous silica, and water as a solvent used per 1 mol of tetraethoxysilane as a silica raw material were each as follows.

[0044] Hexadecyltrimethylammonium chloride: 0.225 mol

[0045] Copper chloride: 0.0204 mol

[0046] Aluminum chloride: 0.0482 mol

[0047] Water: 125 mol

[0048] In addition, for the preparation of the aqueous sodium hydroxide solution as a basic aqueous solution, 0.195 mol of sodium hydroxide was used per 1 mol of tetraethoxysilane as a silica raw material.

[0049] The copper- and aluminum-doped mesoporous silica obtained by the above method had a specific surface area of 1100 m.sup.2 g, and the fine pore diameter was about 2.5 nm (calculated by BJH calculation from the adsorption isotherm of nitrogen gas measured at liquid nitrogen temperature by the multi-point method using BELSORP MAX II manufactured by MicrotracBEL Corp.). In addition, about 50 mg of the copper- and aluminum-doped mesoporous silica was accurately weighed out and dissolved in 4 ml of hydrochloric acid, and then the concentrations of copper and aluminum in the hydrochloric acid solution were measured using an Inductively Coupled Plasma-Optical Emission Spectrometer (ICP-OES manufactured by Thermo Scientific). Based on the measurement results, the copper and aluminum contents in the copper- and aluminum-doped mesoporous silica were calculated. As a result, the copper content was 2.09 wt %, and the aluminum content was 2.00 wt %. The doping of the mesoporous silica with copper and aluminum was confirmed using an X-ray photoelectron spectrometer (K-Alpha Surface Analysis manufactured by Thermo Scientific) and a transmission electron microscope (JEM2010 manufactured by JEOL Ltd.).

Production Reference Example 2: Production of Slurry Containing Copper- and Aluminum-Doped Mesoporous Silica

[0050] In a 250 mL I-Boy PP wide-mouth bottle, 11 g of the copper- and aluminum-doped mesoporous silica produced in Production Reference Example 1, 99 g of water, and 220 g of 2 mm alumina balls were placed. At room temperature, the bottle was put on a ball mill stand and treated at a rotation speed of 180 rpm for 8 hours, and then the alumina balls were removed, thereby giving a slurry in which the content of a copper- and aluminum-doped mesoporous silica having a median diameter of about 0.5 m (the median diameter was measured using a laser diffraction particle size distribution analyzer (SALD-3100 manufactured by Shimadzu Corporation) (same hereinafter)) was 10 wt %.

Production Example 1: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 1)

[0051] In a 250 mL I-Boy PP wide-mouth bottle, 55 g of the slurry obtained in Production Reference Example 2, 11 g of H.C. Polymer 1N (M) from Osaka Organic Chemical Industry Ltd. (containing 20 wt % of polyquaternium-11 having a molecular weight of 500000, Tg: 126 C.), 44 g of water, and 220 g of 2 mm alumina balls were placed. At room temperature, the bottle was put on a ball mill stand and treated at a rotation speed of 90 rpm for 24 hours, and then the alumina balls were removed, thereby giving a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate: 2 wt %).

Production Example 2: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 2)

[0052] In a 250 mL I-Boy PP wide-mouth bottle, 55 g of the slurry obtained in Production Reference Example 2, 22 g of a 10 wt % aqueous solution of Polyvinylpyrrolidene K90 from FUJIFILM Wako Pure Chemical Corporation polyvinylpyrrolidone with undisclosed molecular weight and Tg), 33 g of water, and 220 g of 2 mm alumina balls were placed. At room temperature, the bottle was put on a ball mill stand and treated at a rotation speed of 90 rpm for 24 hours, and then the alumina balls were removed, thereby giving a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of polyvinylpyrrolidone: 2 wt %).

Production Example 3: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 3)

[0053] In the same manner as in Production Example 2 except that Polyvinylpyrrolidone K30 from FUJIFILM Wako Pure Chemical Corporation (polyvinylpyrrolidone with undisclosed molecular weight and Tg) was used instead of Polyvinylpyrrolidone K90 from FUJIFILM Wako Pure Chemical Corporation used in Production Example 2, a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of polyvinylpyrrolidone: 2 wt %) was obtained.

Production Example 4: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 4)

[0054] In the same manner as in Production Example 2 except that 11 g of a 10 wt % aqueous solution of Polyvinylpyrrolidone K90 from FUJIFILM Wako Pure Chemical Corporation and 44 g of water were placed in a 250 mL I-Boy PP wide-mouth bottle, a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of polyvinylpyrrolidone: 1 wt %) was obtained.

Production Example 5: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 5)

[0055] In the same manner as in Production Example 2 except that 44 g of a 10 wt % aqueous solution of Polyvinylpyrrolidone K90 from FUJIFILM Wako Pure Chemical Corporation and 11 g of water were placed in a 250 mL I-Boy PP wide-mouth bottle, a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of polyvinylpyrrolidone: 4 wt %) was obtained.

Production Example 6: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 6)

[0056] In the same manner as in Production Example 1 except that H.C. Polymer 1N (M) from Osaka Organic Chemical Industry Ltd. (containing 20 wt % of polyquaternium-11 having a molecular weight of 500000, Tg: 126 C.) was used instead of H.C. Polymer 1N (M) from Osaka Organic Chemical Industry Ltd. used in Production Example 1, a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate (median diameter: about 0.5 m) (the content of the copper- and a aluminum-doped mesoporous silica: 5 wt %, the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate: 2 wt %) was obtained.

Production Example 7: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 7)

[0057] In the same manner as in Production Example 1 except that H.C. Polymer 2L from Osaka Organic Chemical Industry Ltd. (containing 20 wt % of polyquaternium-11 having a molecular weight of 200000, Tg: 126 C.) was used instead of H.C. Polymer 1N (M) from Osaka Organic Chemical Industry Ltd. used in Production Example 1, a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate: 2 wt %) was obtained.

Production Example 8: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 8)

[0058] In the same manner as in Production Example 1 except that H.C. Polymer 3M from Osaka Organic Chemical Industry Ltd. (containing 20 wt % polyquaternium-11 having a molecular weight of 300000, Tg: 126 C.) was used instead of H.C. Polymer 1N (M) from Osaka Organic Chemical Industry Ltd. used in Production Example 1, a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate: 2 wt %) was obtained.

Production Example 9: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 9)

[0059] In the same manner as in Production Example 1 except that H.C. Polymer 5 from Osaka Organic Chemical Industry Ltd. (containing 20 wt % of polyquaternium-11 having a molecular weight of 150000, Tg: 126 C.) was used instead of H.C. Polymer 1N (M) from Osaka Organic Chemical industry Ltd. used in Production Example 1, a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with a copolymer or vinylpyrrolidone and dimethylaminoethyl methacrylate (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate: 2 wt %) was obtained.

Production Example 10: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 10)

[0060] In the same manner as in Production Example 1 except that H.C. Polymer 5W from Osaka Organic Chemical Industry Ltd. (containing 20 wt % of polyquaternium-11 having a molecular weight of 300000, Tg: 126 C.) was used instead of H.C. Polymer 1N (M) from Osaka Organic Chemical Industry Ltd. used in Product on Example 1, a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate (median diameter: about 0.5 m) (the content of the copper and aluminum-doped mesoporous silica: 5 wt %, the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate: 2 wt %) was obtained.

Production Example 11: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 11)

[0061] In the same manner as in Production Example 2 except that Luviskol K90 from BASF Japan Ltd. (polyvinylpyrrolidone having a molecular weight of 1200000, Tg: undisclosed) was used instead of Polyvinylpyrrolidone K90 from FUJIFILM Wako Pure Chemical Corporation used in Production Example 2, a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of polyvinylpyrrolidone: 2 wt %) was obtained.

Production Example 12: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 12)

[0062] In the same manner as in Production Example 2 except that CREEJUS K-90 from DKS Co. Ltd. (polyvinylpyrrolidone having a molecular weight of 1200000, Tg: undisclosed) was used instead of Polyvinylpyrrolidone K90 from FUJIFILM Wako Pure Chemical Corporation used in Production Example 2, a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of polyvinylpyrrolidone: 2 wt %) was obtained.

Production Example 13: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 13)

[0063] In the same manner as in Production Example 2 except that PVP K-90 from Ashland Inc. (polyvinylpyrrolidone having a molecular weight of 900000, Tg: undisclosed) was used instead of Polyvinylpyrrolidone K90 from FUJIFILM Wako Pure Chemical Corporation used in Production Example 2, a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of polyvinylpyrrolidone: 2 wt %) was obtained.

Production Example 14: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer Suspended in Dispersion Medium (No. 14)

[0064] In the same manner as in Production Example 1 except that Copolymer 845 from Ashland Inc. (containing 20 wt % of a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate having a molecular weight of 1000000, Tg: 172 C.) was used instead of H.C. Polymer 1N (M) from Osaka Organic Chemical Industry Ltd. used in Production Example 1, a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate: 2 wt %) was obtained.

Production Example 15: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Suspended in Dispersion Medium

[0065] At room temperature, 50 g of water was added to 50 g of the slurry obtained in Production Reference Example 2, thereby giving a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %).

Production Example 16: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Dodecylamine Suspended in Dispersion Medium

[0066] In a 250 mL I-Boy PP wide-mouth bottle, 50 g of the slurry obtained in Production Reference Example 2, 1 g of dodecylamine hydrochloride from Tokyo Chemical Industry Co., Ltd., and 49 g of water were placed and, at room temperature, thoroughly shaken and stirred, thereby giving a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface modified with dodecylamine (median diameter: about 0.5 m) (the content of the copper and aluminum-doped mesoporous silica: 5 wt %, the content of dodecylamine: 1 wt %).

Production Example 17: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Mixture of High-Molecular-Weight Block Copolymer and TWEEN-20 Suspended in Dispersion Medium

[0067] In a 250 mL I-Boy PP wide-mouth bottle, 50 g of the slurry obtained in Production Reference Example 2, 0.25 g of DISPERBYK-190 from BYK Japan KK (containing 40 wt % of a high-molecular-weight block copolymer), 0.25 g of TWEEN-20 from FUJIFILM Wako Pure Chemical Corporation, and 49.5 g of water were placed and, at room temperature, thoroughly shaken and stirred, thereby giving a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with a mixture of a high-molecular-weight block copolymer and TWEEN-20 (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of the high-molecular-weight block copolymer: 0.10 wt %, the content of TWEEN-20: 0.25 wt %).

Production Example 18: Production of Slurry of Copper- and Aluminum-Doped Mesoporous Silica Surface-Modified with Silicone Polymer Terminally Modified with Amino Group (Amodimethicone) Suspended in Dispersion Medium

[0068] In the same mariner as an Production Example 2 except that a 10 wt % aqueous solution of amodimethicone prepared by diluting DOWSIL FZ-4671 from Dow Toray Co., Ltd. (containing 31.7 wt % of amodimethicone) with water was used instead of the 10 wt % aqueous solution of Polyvinylpyrrolidone K90 from FUJIFILM Wako Pure Chemical Corporation used in Production Example 2, an attempt was made to give a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica surface-modified with amodimethicone (median diameter: about 0.5 m) (the content of the copper- and aluminum-doped mesoporous silica: 5 wt %, the content of amodimethicone: 2 wt %). However, a purple, sticky, foamy viscous liquid stuck to the inner wall of the bottle and the alumina ball surface, and it was not possible to obtain such a slurry. This was presumably because a plurality of amino groups in amodimethicone caused cross-linking of particles of the copper- and aluminum-doped mesoporous silica, resulting in aggregation and agglomeration.

[0069] The slurries produced in Production Examples 1 to 18 are summarized in Table 1.

TABLE-US-00001 TABLE 1 Metal-Doped Silica Surface Modifier Surface Metal-Doped Content in Molecular Amount Modifier/Metal- Silica Median Slurry Kind Slurry Kind Weight Tg Added Doped Silica Diameter Slurry of Production Cu, Al-doped 5.0 wt % Polyquaternium-11 500000 126 C. 2.0 wt % 40% About 0.5 m Example 1 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Polyvinylpyrrolidone K90 Unknown Unknown 2.0 wt % 40% About 0.5 m Example 2 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Polyvinylpyrrolidone K30 Unknown Unknown 2.0 wt % 40% About 0.5 m Example 3 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Polyvinylpyrrolidone K90 Unknown Unknown 1.0 wt % 20% About 0.5 m Example 4 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Polyvinylpyrrolidone K90 Unknown Unknown 4.0 wt % 80% About 0.5 m Example 5 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Polyquaternium-11 500000 126 C. 2.0 wt % 40% About 0.5 m Example 6 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Polyquaternium-11 200000 126 C. 2.0 wt % 40% About 0.5 m Example 7 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Polyquaternium-11 300000 126 C. 2.0 wt % 40% About 0.5 m Example 8 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Polyquaternium-11 150000 126 C. 2.0 wt % 40% About 0.5 m Example 9 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Polyquaternium-11 300000 126 C. 2.0 wt % 40% About 0.5 m Example 10 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Polyvinylpyrrolidone K90 1200000 Unknown 2.0 wt % 40% About 0.5 m Example 11 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Polyvinylpyrrolidone K90 1200000 Unknown 2.0 wt % 40% About 0.5 m Example 12 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Polyvinylpyrrolidone K90 900000 Unknown 2.0 wt % 40% About 0.5 m Example 13 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Vinyl pyrrolidone/ 1000000 172 C. 2.0 wt % 40% About 0.5 m Example 14 dimethylaminoethyl methacrylate copolymer Slurry of Production Cu, Al-doped 5.0 wt % About 0.5 m Example 15 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % Dodecylamine hydrochloride 221.81 1.0 wt % 20% About 0.5 m Example 16 mesoporous silica Slurry of Production Cu, Al-doped 5.0 wt % DISPERBYK-190 Unknown Unknown 0.35 wt % in 7% in total About 0.5 m Example 17 mesoporous silica TWEEN-20 total Slurry of Production Cu, Al-doped 5.0 wt % Amodimethicone Unknown Unknown 2.0 wt % 40% About 0.5 m Example 18 mesoporous silica (Faulty Production) * Unknown for Molecular Weight and Tg means no information disclosure from the source

Reference Example 1: Analysis of Copper- and Aluminum-Doped Mesoporous Surface-Modified with Polyvinylpyrrolidone Contained in Slurry Produced in Production Examples 2, 4, and 5

[0070] The slurries produced in Production Examples 2, 4, and 5 were each suction-filtered through a 70 mm filter paper, and the copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone was collected on the filter paper. The collected copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone was, without washing with water, dried at 100 C. for about 1 hour and cooled. Subsequently, about 8 mg thereof was weighed out, heated from 40 C. to 600 C. at a heating rate of 5 C./min, and held at 600 C. for 1 hour, and the mass change at the holding time was measured using a thermal analyzer (STA7220 manufactured by Hitachi High-Tech Science Corporation). Supposing that water contained in the copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone evaporates up to 100 C., and polyvinylpyrrolidone adhering to the copper- and aluminum-doped mesoporous silica disappears after 100 C., from the calculation formula ((AB)/A)100 (A: weight before heatingweight loss up to 100 C., B: weight after heating), the proportion of the weight of polyvinylpyrrolidone in the weight of the copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone (measured value: %) was calculated. In addition, from the weight of the copper- and aluminum-doped mesoporous silica and the weight of polyvinylpyrrolidone used in the slurry production, the proportion of the weight of polyvinylpyrrolidone based on their total weight (calculated value: %) was calculated. The measured and calculated values are shown in Table 2.

TABLE-US-00002 TABLE 2 Metal-Doped Silica Surface Modifier Proportion of Surface Modifier Content Amount Measured Calculated Slurry Kind in Slurry Kind Added Value Value Slurry of Production Example 4 Cu, Al-doped mesoporous silica 5.0 wt % Polyvinylpyrrolidone K90 1.0 wt % 18% 17% Slurry of Production Example 2 Cu, Al-doped mesoporous silica 5.0 wt % Polyvinylpyrrolidone K90 2.0 wt % 28% 29% Slurry of Production Example 5 Cu, Al-doped mesoporous silica 5.0 wt % Polyvinylpyrrolidone K90 4.0 wt % 36% 44%

[0071] As is clear from Table 2, in the slurries produced in Production Examples 4 and 2, the proportion of polyvinylpyrrolidone is almost the same between the measured and calculated values. From this, it turned out that at least when the weight of polyvinylpyrrolidone used in the slurry production is up to 0.4 times the weight of the copper- and aluminum-doped mesoporous silica used, the entire amount of polyvinylpyrrolidone adheres to the copper- and aluminum-doped mesoporous silica. On the other hand, in the slurry produced in Production Example 5, the measured value is smaller than the calculated value. From this, it turned out that not the entire amount of polyvinylpyrrolidone used in the slurry production adhered to the copper- and aluminum-doped mesoporous silica, and free polyvinylpyrrolidone was contained in the slurry.

Test Example 1: Evaluation of Dispersibility an Aqueous Solution of Polyquaternium-10

(Evaluation Method)

[0072] 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 (manufactured by Sigma-Aldrich Co. LLC) placed in a glass container, stirred by thorough shaking at room temperature for 10 seconds, and then allowed to stand for 60 minutes. The appearance of the resulting mixture was visually observed, and rated as o when the copper- and aluminum-doped mesoporous silica was kept stably dispersed, or as x when not kept dispersed, forming precipitates.

(Evaluation Results)

[0073] The results are shown in Table 3. As is clear from Table 3, in the visual evaluation of the appearance of the mixture, use of the slurry produced in Production Example 2 resulted in o, while use of the slurry produced in Production Example 15 resulted in x. Thus, it turned out that when a copper- and aluminum-doped mesoporous silica is surface-modified with polyvinylpyrrolidone, and blended into an aqueous solution of polyquaternium-10, the copper- and aluminum-doped mesoporous silica is kept stably dispersed.

Test Example 2: Evaluation of Dispersibility in Aqueous Solution of Polyquaternium-11

(Evaluation Method)

[0074] 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 H.C. Polymer 1N (M) from Osaka Organic Chemical Industry Ltd.) placed in a glass container, stirred by thorough shaking at room temperature for 10 seconds, and then allowed to stand for 60 minutes. The appearance of the resulting mixture was visually observed, and rated as o when the copper- and aluminum-doped mesoporous silica was kept stably dispersed, or as x when not kept dispersed, forming precipitates.

(Evaluation Results)

[0075] The results are shown in Table 3. As is clear from Table 3, in the visual evaluation of the appearance of the mixture, use of the slurries produced in Production Examples 1 to 14 all resulted in o, while use of the slurries produced in Production Examples 15 to 17 all resulted in x. Thus, it turned out that when a copper- and aluminum-doped mesoporous silica 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 kept stably dispersed.

Test Example 3: Evaluation of Dispersibility in Aqueous Dispersion of Amodimethicone

(Evaluation Method)

[0076] 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 Co., Ltd.) placed in a glass container, stirred by thorough shaking at room temperature for 10 seconds, and then allowed to stand for 60 minutes. The appearance of the resulting mixture was visually observed, and rated as o when the copper- and aluminum-doped mesoporous silica was kept stably dispersed, or as x when not kept dispersed, forming precipitates.

(Evaluation Results)

[0077] The results are shown in Table 3. As is clear from Table 3, in the visual evaluation of the appearance of the mixture, use of the slurries produced in Production Examples 1 to 14 all resulted in o, while use of the slurries produced in Production Examples 15 to 17 all resulted in x. Thus, it turned out that when a copper- and aluminum-doped mesoporous silica is surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, or polyvinylpyrrolidone, and blended into an aqueous dispersion of amodimethicone, the copper- and aluminum-doped mesoporous silica is kept stably dispersed.

Test Example 4: Evaluation of Dispersibility in Aqueous Solution of Polyvinylpyrrolidone

(Evaluation Method)

[0078] 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 Luviskol K90 from BASE Japan Ltd.) placed in a glass container, stirred by thorough shaking at room temperature for 10 seconds, and then allowed to stand for 60 minutes. The appearance of the resulting mixture was visually observed, and rated as o when the copper- and aluminum-doped mesoporous silica was kept stably dispersed, or as x when not kept dispersed, forming precipitates.

(Evaluation Results)

[0079] The results are shown in Table 3. As is clear from Table 3, in the visual evaluation of the appearance of the mixture, use of the slurry produced in Production Example 2 resulted in o, while use of the slurry produced in Production Example 15 resulted in x. Thus, it turned out that when a copper- and aluminum-doped mesoporous silica is surface-modified with polyvinylpyrrolidone, and blended into an aqueous solution of polyvinylpyrrolidone, the copper- and aluminum-doped mesoporous silica is kept stably dispersed.

Test Example 5: Evaluation of Adsorption Action on Cysteamine

(Evaluation Method)

[0080] 1.8 mL of water was added to a centrifuge tube containing 0.1 mL of each of the slurries produced in Production Examples 1 to 17, and thoroughly shaken at room temperature to make a uniform dispersion. Subsequently, 0.1 mL of as aqueous cysteamine solution having a concentration of 5.86 wt % was further added, thoroughly shaken for 30 seconds, and then centrifuged for 90 seconds. After that, the supernatant was taken out from the centrifuge tube and measured for absorbance at 235 nm. From the calibration curve of the concentration of the aqueous cysteamine solution and the absorbance, the cysteamine concentration of the supernatant was determined, and, from the calculation formula ((0.293 wt %cysteamine concentration of supernatant)/0.293 wt %)100, the adsorption rate (%) of each of the slurries produced in Production Examples 1 to 17 on cysteamine was calculated. Incidentally, the absorbance was measured using a Corona Grating Microplate Reader SH-1000 from Corona Electric Co., Ltd.

(Evaluation Results)

[0081] The results are shown in Table 3. As is clear from Table 3, all the slurries produced in Production Examples 1 to 17 had high adsorption on cysteamine, and no decrease in the adsorption on cysteamine due to the surface modification of the copper- and aluminum-doped mesoporous silica with a surface modifier was observed.

Reference Example 2: Zeta Potential of Slurry Produced in Production Examples 1 to 17

[0082] Measurement was performed in a zeta potential/particle size/molecular weight measurement system (ELSZ-2000ZS) from Otsuka Electronics Co., Ltd. The results are shown in Table 3. In general, the greater the absolute value of the zeta potential, the greater the electrostatic repulsive force and the higher the dispersion stability. In fact, the slurry produced in Production Example 15 is a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica, and the absolute value of the zeta potential is 30 mV or more. However, even in the case of such a slurry having uniformly dispersed therein a copper- and aluminum-doped mesoporous silica, when blended into an aqueous solution or aqueous dispersion of a cationic polymer such as polyquaternium-10, polyquaternium-11, or amodimethicone, charge compensation occurs between the negatively charged copper- and aluminum-doped mesoporous silica and the cationic polymer, and, as a result, cross-linking occurs due to the adsorption of the two, etc., resulting in aggregation and agglomeration, causing precipitation. In contrast, with respect to the slurries produced in Production Examples 1 to 14, although the absolute value of the zeta potential of each slurry is smaller than the absolute value of the zeta potential of the slurry produced in Production Example 15, and the electrostatic repulsive force is smaller, the dispersion stability in the slurry is high. This is presumably attributable to the repulsive force due to the high steric hindrance of the vinylpyrrolidone unit-containing polymer present on the surface of the copper- and aluminum-doped mesoporous silica, and it is considered that even after the slurry is blended into an aqueous solution or aqueous dispersion of a cationic polymer, this repulsive force inhibits agglomeration and agglomeration with the cationic polymer, contributing to the maintenance of dispersion stability. The reason why the slurries produced in Production Examples 16 and 17 cannot maintain dispersion stability after being blended into an aqueous solution or aqueous dispersion of a cationic polymer is presumably because unlike a vinylpyrrolidone unit-containing polymer, the surface modifier used has a chemical structure that does not bring about repulsive force due to high steric hindrance. The reason why precipitation occurs as a result of blending the slurry produced in Production Example 15 into an aqueous solution of a nonionic polymer polyvinylpyrrolidone is presumably not because of the charge compensation as described above, and is not necessarily clear. However, the reason why no precipitation occurs as a result of blending the slurry produced in Production Example 2 is presumably attributable, again, to the repulsive force due to the high steric hindrance of polyvinylpyrrolidone present on the surface of the copper- and aluminum-doped mesoporous silica.

TABLE-US-00003 TABLE 3 Dispersibility in Cosmetic Product Raw Material Polymer Liquid Surface Modifier Poly- Poly- Amodi- Polyvinyl- Cysteamine Zeta Amount quaternium-10 quaternium-11 methicone pyrrolidone Adsorption Potential Slurry Kind Added Liquid Liquid Liquid Liquid Rate (mV) Examples Slurry of Polyquaternium-11 2.0 wt % Not performed Not performed 96.0% 4.25 Production Example 1 Slurry of Polyvinyl- 2.0 wt % 96.3% 2.69 Production pyrrolidone K90 Example 2 Slurry of Polyvinyl- 2.0 wt % Not performed Not performed 96.0% 11.07 Production pyrrolidone K30 Example 3 Slurry of Polyvinyl- 1.0 wt % Not performed Not performed 96.2% 4.35 Production pyrrolidone K90 Example 4 Slurry of Polyvinyl- 4.0 wt % Not performed Not performed 96.1% 0.69 Production pyrrolidone K90 Example 5 Slurry of Polyquaternium-11 2.0 wt % Not performed Not performed 96.0% 15.37 Production Example 6 Slurry of Polyquaternium-11 2.0 wt % Not performed Not performed 96.0% 1.42 Production Example 7 Slurry of Polyquaternium-11 2.0 wt % Not performed Not performed 96.0% 31.12 Production Example 8 Slurry of Polyquatemium-11 2.0 wt % Not performed Not performed 96.0% 2.69 Production Example 9 Slurry of Polyquaternium-11 2.0 wt % Not performed Not performed 96.0% 1.35 Production Example 10 Slurry of Polyvinyl- 2.0 wt % Not performed Not performed 96.0% 1.07 Production pyrrolidone K90 Example 11 Slurry of Polyvinyl- 2.0 wt % Not performed Not performed 96.0% 0.30 Production pyrrolidone K90 Example 12 Slurry of Polyvinyl- 2.0 wt % Not performed Not performed 96.0% 0.70 Production pyrrolidone K90 Example 13 Slurry of Vinyl pyrrolidone/ 2.0 wt % Not performed Not performed 96.0% 1.13 Production dimethylaminoethyl Example 14 methacrylate copolymer Comparative Slurry of X X X X 96.0% 34.73 Examples Production Example 15 Slurry of Dodecylamine 1.0 wt % Not performed X X Not performed 95.7% 4.32 Production hydrochloride Example 16 Slurry of DISPERBYK-190 0.35 wt % Not performed X X Not performed 96.1% 15.38 Production TWEEN-20 in total Example 17 Slurry of Amodimethicone 2.0 wt % Not performed Not Not Not performed Not Not Production performed performed performed performed Example 18 (Faulty Production)

Application Example 1: Production of Perm Treatment Agent Having Blended Therein Metal-Doped Porous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer

[0083] The slurry containing a 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, and thoroughly stirred at room temperature. As a result, it was possible to produce a perm treatment agent having uniformly dispersed therein, at a content of 0.5 wt %, a copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate.

Application Example 2: Production of Shampoo Agent Having Blended Therein Metal-Doped Porous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer

[0084] The slurry containing a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone obtained in Production Example 2 was added to a commercially available shampoo agent containing at least polyquaternium-10, and thoroughly stirred at room temperature. As a result, it was possible to produce a shampoo agent having uniformly dispersed therein, at a content of 0.5 wt %, a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone.

Application Example 3: Production of Hair Treatment Agent Having Blended Therein Metal-Doped Porous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer

[0085] The slurry containing a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone obtained in Production Example 2 was added to a commercially available hair treatment agent containing at least amodimethicone, and thoroughly stirred at room temperature. As a result, it was possible to produce a hair treatment agent having uniformly dispersed therein, at a content of 0.5 wt %, a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone.

Application Example 4: Production of Hair Styling Agent Having Blended Therein Metal-Doped Porous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer

[0086] The slurry containing a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone obtained in Production Example 2 was added to a commercially available hair styling agent containing at least polyvinylpyrrolidone, and thoroughly stirred at room temperature. As a result, it was possible to produce a hair styling agent having uniformly dispersed therein, at a content of 0.5 wt %, a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone.

Application Example 5: Production of Toilet Seat Cleaner Having Blended Therein Metal-Doped Porous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer

[0087] The slurry containing a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone obtained in Production Example 2 was added to a commercially available toilet seat cleaner containing at least polyquaternium-55, and thoroughly stirred at room temperature. As a result, it was possible to produce a toilet seat cleaner having uniformly dispersed therein, at a content of 0.5 wt %, a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone.

Application Example 6: Production of Alcoholic Hand Gel Having Blended Therein Metal-Doped Porous Silica Surface-Modified with Vinylpyrrolidone Unit-Containing Polymer

[0088] The slurry containing a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone obtained in Production Example 13 was added to a commercially available alcoholic hand gel containing at least carbomer, and thoroughly stirred at room temperature. As a result it was possible to produce an alcoholic hand gel having uniformly dispersed therein, at a content of 0.5 wt %, a copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone.

INDUSTRIAL APPLICABILITY

[0089] The present invention makes it possible to provide a metal-doped porous silica that can be blended into an article, for example, a cosmetic product such as a perm treatment agent, and kept stably dispersed therein. In this respect, the present invention is industrially applicable.