hair treatment agent

Abstract

To provide hair treatment agents that have an excellent hair deodorant effect and texture after perm treatment and the like and in which a copper-doped porous silica is blended so as to be stably dispersed and maintained.SOLUTION: The hair treatment agent of the present invention comprises a copper-doped porous silica surface-modified with a polymer containing a vinylpyrrolidone unit. Specific examples of the polymer containing the vinylpyrrolidone unit include a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, polyvinylpyrrolidone, and the like.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a hair treatment agent that has an excellent deodorizing effect and texture for hair after a perm treatment or the like. [Background technology]

[0002] It is well known that there is a high demand for perm treatments such as straight perm treatments and permanent wave treatments not only among young women but also among older women and men. Perm treatments are typically performed in a two-step process using a first agent containing a reducing agent and a second agent containing an oxidizing agent. The reducing agent in the first agent cleaves the cystine bonds (SS bonds) in the hair, and then the oxidizing agent in the second agent rebonds the cystine bonds that were cleaved. However, in recent years, a one-step process (acid heat treatment) has also been proposed, which forms new chemical bonds in the hair without cleaving the cystine bonds, thereby deforming and fixing the hair. In the former method, the reducing agent contained in the first agent is a substance with a thiol group, such as cysteamine, L-cysteine, thioglycolic acid, butyrolactone thiol, thiolactic acid, thioglycerin, or glyceryl thioglycolate, while in the latter method, glyoxylic acid analogues such as glyoxyloyl carbocysteine ​​or glyoxyloyl keratin amino acid are used. However, since both of these are sulfur-containing substances, the sulfur-containing odor emitted by the substance itself or its decomposition products remains in the hair after treatment, and various methods have been proposed to eliminate this odor. The present inventors have also reported in Patent Documents 1 and 2 that copper-doped porous silica exhibits excellent deodorizing effects against sulfur-containing odors. However, in order for copper-doped porous silica to fully exert its deodorizing effects on hair after a perm treatment or an acid-heat treatment, it is essential to incorporate copper-doped porous silica into a perm treatment agent or an acid-heat treatment agent so that it remains stably dispersed. In addition, it is necessary to ensure that incorporating copper-doped porous silica into such treatment agents does not result in a deterioration in the texture of the hair after the treatment. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-14656 [Patent Document 2] Japanese Patent Publication No. 2020-15640 Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, an object of the present invention is to provide a hair treatment agent that has an excellent deodorizing effect and texture for hair after perming, etc., and that contains copper-doped porous silica formulated so that it is stably dispersed and maintained. [Means for solving the problem]

[0005] In view of the above, the present inventors have conducted extensive research and found that when copper-doped porous silica is surface-modified with a polymer containing vinylpyrrolidone units and then incorporated into a perm treatment agent, the copper-doped porous silica can be stably dispersed and maintained in the perm treatment agent, and that when a perm treatment agent containing copper-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units is used to perform a perm, the deodorizing effect on hair after the perm treatment is excellent, and that when this perm treatment agent is used to perform a perm, the texture of the hair after the perm treatment is excellent.Furthermore, the present inventors have found that similar results can be obtained when copper-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units is incorporated into an acid-heat treatment agent, or when it is incorporated into shampoos, treatments, and styling agents used after perm treatment or acid-heat treatment.

[0006] The hair treatment agent of the present invention, which has been developed based on the above findings, comprises, as set forth in claim 1: At least one copolymer selected from the group consisting of a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate and polyvinylpyrrolidoneThe composition contains copper-doped porous silica whose surface has been modified with a polymer containing a vinylpyrrolidone unit. The hair treatment composition according to claim 2 is the hair treatment composition according to claim 1, wherein the porous silica is further doped with aluminum. 。 Ma and claims 3 The hair treatment agent according to claim 1 or 2 In the hair treatment composition described above, the copper-doped porous silica whose surface has been modified with a polymer containing a vinylpyrrolidone unit is blended in an amount of 0.01 to 5 wt % in the hair treatment composition. Also, claims 4 The hair treatment composition according to claims 1 to 5 3 The hair treatment agent according to any one of the above items 1 to 4, further comprising a plant extract. Also, claims 5 The hair treatment composition according to claims 1 to 5 4 The hair treatment agent according to any one of the above items is any one of a perm treatment agent, an acid heat treatment agent, a shampoo, a treatment agent, and a styling agent. The method for producing the hair treatment agent of the present invention further comprises the steps of: 6 As stated, At least one copolymer selected from the group consisting of a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate and polyvinylpyrrolidone The method includes a step of adding a slurry obtained by suspending copper-doped porous silica, the surface of which has been modified with a polymer containing a vinylpyrrolidone unit, in a dispersion medium at any point in the process of producing a hair treatment agent. The perm method or acid heat treatment method of the present invention is as follows: 7 As described above, claims 1 to 5 The hair treatment is carried out using the hair treatment agent according to any one of the items above. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a hair treatment agent which has an excellent deodorizing effect and texture for hair after a perm treatment or the like, and which contains copper-doped porous silica blended so that it is stably dispersed and maintained. DETAILED DESCRIPTION OF THE INVENTION

[0008] The hair treatment agent of the present invention contains copper-doped porous silica whose surface has been modified with a polymer containing a vinylpyrrolidone unit.

[0009] In the present invention, the copper-doped porous silica may be, for example, that described by the present inventors in JP 2020-15640 A. Here, "copper-doped porous silica" refers to porous silica in which copper is chemically bonded and incorporated into the inorganic network consisting of siloxane bonds that constitute the porous silica. Specifically, it is as follows.

[0010] The copper content in the copper-doped porous silica is, for example, 0.01 to 10 wt%, preferably 0.1 to 5 wt%. If the copper content in the copper-doped porous silica is less than 0.01 wt%, there is a risk that a sufficient deodorizing effect on the sulfur-containing odors emitted by sulfur-containing substances contained in perm treatment agents and acid heat treatment agents and their decomposition products may not be obtained, while porous silica doped with copper in an amount exceeding 10 wt% may be difficult to produce.

[0011] An example of porous silica is mesoporous silica in which pores (mesopores) having a diameter of 2 to 50 nm are regularly arranged.

[0012] The specific surface area of ​​porous silica is, for example, 500 to 2000 m 2 / g is preferable in terms of maintaining durability.

[0013] Copper-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.

[0014] (Process 1) First, a surfactant and raw materials for doping copper 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.

[0015] 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.

[0016] 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.

[0017] The amount of raw material dissolved in the solvent for doping copper into mesoporous silica 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.

[0018] As a raw material for doping copper into mesoporous silica, for example, copper nitrate or copper chloride is preferably used. The raw materials for doping copper may be used alone or in combination of two or more.

[0019] 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.

[0020] (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.

[0021] 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.

[0022] (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 copper 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.

[0023] (Step 4) Finally, the surfactant micelles obtained in step 3, which form an inorganic network on the surface composed of siloxane bonds that constitute the mesoporous silica and to which copper is chemically bonded, are filtered and recovered as a precipitate. The precipitate is 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 copper-doped mesoporous silica. The copper-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 allows for easy and stable dispersion in perm treatments and acid-heat treatments).

[0024] The addition of the raw material to the system for doping copper into mesoporous silica is not limited to the above-mentioned step 1 in which the raw material is 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 material is 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.

[0025] The copper-doped porous silica may be doped with a metal other than copper. A specific example of the metal other than copper is aluminum, which has the effect of increasing the durability of the porous silica. The aluminum content in the copper-doped porous silica is, for example, 0.01 to 10 wt%, preferably 0.1 to 5 wt%, and more preferably the total amount including the copper content is up to 10 wt%.

[0026] An example of a method for doping porous silica with aluminum together with copper is the method for producing copper-doped mesoporous silica described above, in which the raw material (e.g., aluminum chloride) is dissolved in a solvent or solution together with the raw material for doping mesoporous silica with copper. The amount of raw material for doping mesoporous silica with aluminum dissolved in the solvent or solution is, for example, 0.001 to 0.5 mol, preferably 0.01 to 0.1 mol, per mol of silica raw material added in step 2. However, it is more preferable that the total amount, including the amount of raw material for doping mesoporous silica with copper dissolved in the solvent or solution, is a maximum of 0.5 mol per mol of silica raw material.

[0027] In the present invention, a polymer containing a vinylpyrrolidone unit is used to surface modify copper-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, and a specific example thereof is a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. The copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate is advantageous in that its quaternary ammonium salt is already used as a cosmetic raw material under the cosmetic name Polyquaternium-11. The polymer containing a vinylpyrrolidone unit may also be polyvinylpyrrolidone. Polyvinylpyrrolidone is also advantageous in that it is already used as a cosmetic raw material. In consideration of adhesion to copper-doped porous silica and ease of surface modification, the preferred molecular weight of the polymer containing a 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.

[0028] The method for surface-modifying copper-doped porous silica with a polymer containing vinylpyrrolidone units is not particularly limited. It can be performed by mixing and stirring the copper-doped porous silica and the polymer containing vinylpyrrolidone units, adjusting the temperature as necessary. A preferred method involves suspending copper-doped porous silica in a dispersion medium, placing the resulting slurry in a treatment vessel together with the polymer containing vinylpyrrolidone units and balls (media) used in a ball mill (and optionally containing a dispersion medium), and then rotating the treatment vessel containing these components on a ball mill stand (for example, at a rotation speed of 15 to 500 rpm). This method easily produces copper-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units in a form that is highly dispersible in perm treatment agents and acid-heat treatment agents. The ball milling time is, for example, 1 to 50 hours, preferably 6 to 30 hours. Water can be used as the dispersion medium for the slurry in which copper-doped porous silica is suspended, or as a dispersion medium that may be further contained in the treatment container. 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 copper doped in the porous silica may dissolve, while if the pH of the dispersion medium is above 11, the porous silica may dissolve. Furthermore, considering the effect on the stability of the perm treatment agent, it is undesirable for the pH of the dispersion medium to be too acidic or too alkaline, and considering the effect on the stability of the acid-heat treatment agent, it is undesirable for the pH of the dispersion medium to be too alkaline.

[0029] The amounts of copper-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 relative to the weight of the copper-doped porous silica is too small, the effect of surface-modifying the former with the latter cannot be fully achieved, and dispersibility in perm treatments and acid-heat treatments may be reduced. By limiting the weight of the polymer containing vinylpyrrolidone units to 0.5 times the weight of the copper-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 copper-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 copper-doped porous silica be 2 times. Slurries containing a large amount of polymers containing free vinylpyrrolidone units are highly viscous and difficult to handle. In addition, adding such slurries to permanent wave treatment agents or acid-heat treatment agents may affect their compositions. From the viewpoint of ease of handling, the content of copper-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units in the slurry is preferably, for example, 0.1 to 10 wt %. The balls used in the ball mill (e.g., alumina balls or zirconia balls with a diameter of 1 to 5 mm) are preferably used in a number that is 1 to 5 times the total weight of the copper-doped porous silica, the polymer containing vinylpyrrolidone units, and the dispersion medium.

[0030] Perm treatment agents containing copper-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units may be used for straight perm treatment or permanent wave treatment. When copper-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units is used in a two-stage perm treatment, the first agent may contain a reducing agent such as cysteamine, L-cysteine, thioglycolic acid, butyrolactone thiol, thiolactic acid, thioglycerin, or glyceryl thioglycolate; the second agent may contain an oxidizing agent such as hydrogen peroxide or bromate; or the intermediate or post-treatment agent may contain neither a reducing agent nor an oxidizing agent. The formulation of perm treatment agents or acid-heat treatment agents containing copper-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units may be, for example, liquid or cream. The amount of copper-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units in a perm treatment agent or an acid-heat treatment agent is preferably 0.01 to 5 wt%, more preferably 0.02 to 0.5 wt%. If the amount of copper-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units in these agents is too small, the deodorizing effect of the copper-doped porous silica on hair after treatment may be reduced. On the other hand, if the amount of copper-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units in these agents is too large, the texture of the hair after treatment may be reduced or rinsing may be difficult. The copper-doped porous silica, which has been surface-modified with a polymer containing vinylpyrrolidone units, can be blended into a permanent wave treatment agent or an acid heat treatment agent, for example, by adding a slurry, which is prepared by suspending copper-doped porous silica, which has been surface-modified with a polymer containing vinylpyrrolidone units, in a dispersion medium, at any point in the process of producing these agents.

[0031] Furthermore, perm treatment agents and acid-heat treatment agents containing copper-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units may also contain plant extracts, which have traditionally been incorporated into these agents for the purpose of deodorizing or masking odors. The combined use of copper-doped porous silica surface-modified with a polymer containing vinylpyrrolidone units and plant extracts can effectively deodorize sulfur-containing odors remaining in hair after perm treatment or acid-heat treatment, as well as deodorize or mask sweat odors containing acetic acid and ammonia, aging odors containing nonenal, and scalp odors containing medium- to long-chain fatty acids. The plant extract may be an extract obtained by extracting components with deodorizing or masking properties contained in a single plant, or a mixture of extracts derived from multiple plants. Specific examples include rose extract, sugarcane extract, and herbal extract, and these can be commercially available in powder or liquid form as deodorizing or masking materials. Commercially available rose extracts include, for example, Taiyo Fragrance's Rose Clean (a powdered product consisting of 10 wt% Gallica rose extract, 45 wt% dextrin, and 45 wt% cyclodextrin). Commercially available sugarcane extracts include, for example, Mitsui Sugar Co., Ltd.'s MSX-245 sugarcane extract (a liquid product consisting of 0.02 wt% sugarcane extract, 45.00 wt% ethanol, and 54.98 wt% water). Commercially available herbal extracts include, for example, Ogawa Fragrance's Mixed Plant Extract OG-D1 (a liquid product consisting of 1.11 wt% mixed plant extract (five herbal medicines: Angelica sinensis, Peony root, Cnidium root, Rehmannia glutinosa, and Ginger root), 49.445 wt% ethanol, and 49.445 wt% water). The amount of plant extract blended into perm treatment agents or acid-heat treatment agents is, for example, preferably 0.0001 to 0.1 wt%, more preferably 0.0005 to 0.05 wt%, for rose extract, for example, preferably 0.000002 to 0.001 wt%, more preferably 0.000004 to 0.0002 wt%, for sugarcane extract, for example, preferably 0.000111 to 0.0555 wt%, more preferably 0.000222 to 0.0111 wt%, for herbal extract.

[0032] In the above, perm treatment agents and acid heat treatment agents have been described as examples of hair treatment agents containing copper-doped porous silica that has been surface-modified with a polymer containing vinylpyrrolidone units, but copper-doped porous silica that has been surface-modified with a polymer containing vinylpyrrolidone units may also be incorporated into hair treatment agents such as shampoos, treatment agents, and styling agents that are used for straightening, maintaining the condition, improving the texture, etc. of hair after perm treatment or acid heat treatment. Copper-doped porous silica that has been surface-modified with a polymer containing vinylpyrrolidone units can be incorporated into these hair treatment agents in the same manner as in the case of incorporation into perm treatment agents and acid heat treatment agents, and this can deodorize any sulfur-containing odor remaining in the hair after treatment and improve the texture of the hair. [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 2 The 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] Production Example 2: Production of a slurry in which copper- and aluminum-doped mesoporous silica is suspended in a dispersion medium 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 produced in Reference Manufacturing Example 2, 11 g of Osaka Organic Chemical Industry's HC Polymer 1N(M) (containing 20 wt% of polyquaternium-11 with a molecular weight of 500,000), 44 g of water, and 220 g of 2 mm diameter alumina balls. The bottle was then 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 produced in Reference Manufacturing Example 2, 22 g of a 10 wt % aqueous solution of BASF Japan's Rubiscol K90 (polyvinylpyrrolidone with a molecular weight of 1,200,000), 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 (copper and aluminum doped mesoporous silica content: 5 wt %, polyvinylpyrrolidone content: 2 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.

[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 K90 (polyvinylpyrrolidone of undisclosed molecular weight) manufactured by Fujifilm Wako Pure Chemical Industries was used instead of Rubiscol K90 manufactured by BASF Japan. 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 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 of undisclosed molecular weight) manufactured by Fujifilm Wako Pure Chemical Industries was used instead of Luviscol K90 manufactured by BASF Japan. The slurry was surface-modified with polyvinylpyrrolidone and uniformly dispersed with copper- and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm).

[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 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 3 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.

[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 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, Ltd.) and 11 g of water, in the same manner as in Production Example 3, 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.

[0044] Production Example 7: Production of a slurry in which copper and aluminum doped mesoporous silica is suspended in a dispersion medium The copper- and aluminum-doped mesoporous silica produced in Reference Production Example 1 was pulverized in a mixer to a median diameter of approximately 30 μm, and 104.5 g of water was added to 5.5 g of the pulverized silica. The mixture was shaken vigorously at room temperature to obtain a slurry (content of copper- and aluminum-doped mesoporous silica: 5 wt%) in which the copper- and aluminum-doped mesoporous silica (median diameter: approximately 30 μm) was uniformly dispersed.

[0045] Production Example 8: 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 produced 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 (content of copper- and aluminum-doped mesoporous silica: 5 wt %, content of dodecylamine: 1 wt %) in which copper- and aluminum-doped mesoporous silica (median diameter: approximately 0.5 μm) that had been surface-modified with dodecylamine was uniformly dispersed.

[0046] Preparation Example 9: 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 produced in Production Reference 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 stirred vigorously 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%).

[0047] The slurries produced in Production Examples 1 to 9 are summarized in Table 1.

[0048] [Table 1]

[0049] Test Example 1: Evaluation of dispersibility of perm treatment agents (Evaluation method) 0.5 mL of each of the slurries produced in Production Examples 1 to 9 and 1.5 mL of water were added to 8 mL of a test solution containing 1.25 times the concentration of each ingredient of CosmeCurl Prism Plus After Lotion, the second agent from Arimino, placed in a glass container. The mixture was stirred by shaking vigorously for 10 seconds at room temperature and then allowed to stand for 90 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 it was not dispersed and a precipitate had formed.

[0050] In addition, using a stability tester (ST-1 manufactured by Eiko Seiki Co., Ltd.), the backscattered light intensity of the mixed liquid in an area approximately 3 mm high from the bottom of the glass container was measured every 3 minutes from immediately after adding the slurry and water to the test liquid and stirring until 90 minutes had elapsed.The integrated value of the difference between the measured value immediately after stirring and the measured value every 3 minutes was calculated as the peak area value, and the degree of precipitation was evaluated by quantifying it.

[0051] (Evaluation results) The results are shown in Table 2. As is clear from Table 2, in a visual evaluation of the appearance of the mixed liquid, all of the slurries produced in Production Examples 1 to 6 were rated as ○, while all of the slurries produced in Production Examples 7 to 9 were rated ×. Furthermore, in an evaluation in which the degree of precipitation was quantified, the peak area values ​​when the slurries produced in Production Examples 1 to 6 were used were 3.0 or less, whereas the peak area values ​​when the slurries produced in Production Examples 7 to 9 were used were greater than 10. Therefore, it was found that when copper- and aluminum-doped mesoporous silica was surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate or polyvinylpyrrolidone and then blended into a perm treatment agent, a perm treatment agent in which the copper- and aluminum-doped mesoporous silica was stably dispersed and maintained could be obtained.

[0052] Test Example 2: 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 9, 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 tubes, 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 9 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.

[0053] (Evaluation results) The results are shown in Table 2. As is clear from Table 2, all of the slurries produced in Production Examples 1 to 9 had high adsorption rates for cysteamine, and no decrease in the adsorption rate for cysteamine was observed due to surface modification of the copper- and aluminum-doped mesoporous silica with a surface modifier.

[0054] Reference Example 1: Zeta potential of slurries produced in Production Examples 1 to 9 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 2. 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 7, in which copper- and aluminum-doped mesoporous silica was uniformly dispersed, had an absolute value of zeta potential of 30 mV or greater. However, even in this slurry, in which copper- and aluminum-doped mesoporous silica was uniformly dispersed, when it was blended with a permanent treatment agent containing various components, particularly a cationic polymer such as polyquaternium-11, the negatively charged copper- and aluminum-doped mesoporous silica and the cationic component contained in the permanent treatment agent cancel each other out, resulting in cross-linking due to adsorption, aggregation, and agglomeration, resulting in precipitation (the second agent test solution used in Test Example 1 contained polyquaternium-11). In contrast, the slurries produced in Production Examples 1 to 6 all had smaller absolute zeta potentials than the slurry produced in Production Example 7. 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 polymer containing vinylpyrrolidone units present on the surface of the copper- and aluminum-doped mesoporous silica. This repulsive force contributes to maintaining dispersion stability even after being incorporated into a perm treatment agent by inhibiting aggregation and agglomeration with the components contained in the perm treatment agent. The reason the slurries produced in Production Examples 8 and 9 were unable to maintain dispersion stability after being incorporated into a perm treatment agent is thought to be because the surface modifiers used had chemical structures that did not produce repulsive forces due to high steric hindrance, such as the polymer containing vinylpyrrolidone units.

[0055] [Table 2]

[0056] Test Example 3: Evaluation of the practicality of perm treatment agent (first agent) (Part 1) (Evaluation method) Cysteamine hydrochloride, diethylenetriaminepentaacetic acid pentasodium solution, 28% ammonia water, polyquaternium-11, rose extract powder (Taiyo Fragrance's Rose Clean, which contains 10 wt% Gallica rose extract), sugarcane extract liquid (Mitsui Sugar Co., Ltd.'s sugarcane extract MSX-245, which contains 0.02 wt%), herbal extract liquid (Ogawa Fragrance's mixed plant extract, which contains 1.11 wt% of five herbal medicines: Angelica sinensis, Peony root, Cnidium root, Rehmannia glutinosa, and Ginger root) A first-agent model solution of various compositions shown in Table 3, which was prepared at room temperature using Extract OG-D1), the slurry produced in Production Example 2, the slurry produced in Production Example 7, and purified water, and a second-agent model solution of the composition shown in Table 3, which was prepared at room temperature using sodium bromate, pentasodium diethylenetriaminepentaacetate solution, 89% phosphoric acid, sodium hydroxide, and purified water, were used to perm strands of Japanese hair according to the perm treatment process published by Arimino, and the deodorizing effect on the unpleasant lingering odor of the hair after treatment and the texture of the hair were evaluated. The evaluation of the deodorizing effect on the unpleasant lingering odor of the hair was performed according to the following criteria after towel drying (wet hair), after drying (dry hair), and the day after treatment. ◎◎: Has a pleasant scent with no unpleasant lingering odor ◎: No unpleasant lingering odor ○: There is a slight unpleasant odor, but it is within the acceptable range. △: Unpleasant lingering odor ×: Strong unpleasant lingering odor The texture of the hair was evaluated based on whether it felt smooth to the touch after treatment. Furthermore, when the first agent model solution was prepared, its appearance was visually inspected to determine whether or not any precipitation occurred.

[0057] (Evaluation results) The results are shown in Table 3. As is clear from Table 3, when perming was performed using the first agent model solutions of Examples 1 to 7, which contained the slurry produced in Production Example 2 (copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone, with a content of 0.035 wt% in Examples 1 and 3 to 7, and 0.14 wt% in Example 2), a deodorizing effect was obtained against the unpleasant lingering odor of hair after perming, and this effect continued until the day after perming. The hair also had an excellent texture. This was thought to be due to the presence of polyvinylpyrrolidone on the surface, which reduced the surface roughness of the copper- and aluminum-doped mesoporous silica and reduced static electricity that could occur between the silica and hair. By combining copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone with rose extract-containing powder, sugarcane extract-containing liquid, and herbal extract-containing liquid, which are known as odor-deodorizing and masking materials, an improved deodorizing effect was observed against unpleasant lingering odors in hair after treatment. Excellent results were obtained when performing a perm treatment using the first agent model solution of Example 3 combined with all of these materials. Furthermore, the first agent model solutions of Examples 1 to 7, which contain the slurry produced in Production Example 2, did not exhibit any precipitation during preparation, despite the inclusion of polyquaternium-11, because the copper- and aluminum-doped mesoporous silica contained in the slurry produced in Production Example 2 was surface-modified with polyvinylpyrrolidone. When performing a perm treatment using the first agent model solution of Comparative Example 1, which does not contain the slurry produced in Production Example 2, the slurry produced in Production Example 7, or a plant extract, no deodorizing effect against unpleasant lingering odors in hair after treatment was obtained. When a perm treatment was performed using the first agent model solution of Comparative Example 2 containing the slurry produced in Production Example 7, a deodorizing effect was obtained against the unpleasant lingering odor of the hair after the treatment, but the copper- and aluminum-doped mesoporous silica contained in the slurry produced in Production Example 7 was not surface-modified with polyvinylpyrrolidone, and therefore the texture of the hair was not excellent. Furthermore, when the first agent model solution was prepared, the formation of precipitation was observed.When a perm treatment was performed using the first agent model liquid of Comparative Example 3, which contained a rose extract-containing powder instead of the slurry produced in Production Example 2, a deodorizing effect on the unpleasant lingering odor of the hair after the treatment was observed, but the duration of the deodorizing effect did not reach the effect of a perm treatment using the first agent model liquids of Examples 1 to 7, which contained the slurry produced in Production Example 2. When a perm treatment was performed using the first agent model liquid of Comparative Example 4, which contained a sugarcane extract-containing liquid instead of the slurry produced in Production Example 2, the deodorizing effect on the unpleasant lingering odor of the hair after the treatment was inferior to the effect of a perm treatment using the first agent model liquids of Examples 1 to 7, which contained the slurry produced in Production Example 2, at all evaluation points.

[0058] [Table 3]

[0059] Test Example 4: Evaluation of the practicality of perm treatment agent (second agent) (Part 1) (Evaluation method) The first agent model solution, which was prepared at room temperature using cysteamine hydrochloride, diethylenetriaminepentaacetic acid pentasodium solution, 28% aqueous ammonia, and purified water, had the composition shown in Table 4, and the second agent model solution, which was prepared at room temperature using sodium bromate, diethylenetriaminepentaacetic acid pentasodium solution, 89% phosphoric acid, sodium hydroxide, polyquaternium-11, rose extract powder (Rose Clean from Taiyo Fragrance Co., Ltd., which contains 10 wt% Gallica rose extract), and sugarcane extract liquid (Sugarcane Extract from Mitsui Sugar Co., Ltd., which contains 0.02 wt% sugarcane extract). The perm treatment was carried out on Japanese hair strands according to the perm treatment process published by Arimino, using various formulations shown in Table 4, including a liquid containing a herbal extract (Ogawa Fragrance Co., Ltd.'s mixed plant extract OG-D1, containing 1.11 wt% of mixed plant extract (five herbal medicines: Angelica sinensis, Peony root, Cnidium root, Rehmannia glutinosa, and Ginger)), the slurry produced in Production Example 2, the slurry produced in Production Example 7, and a second agent model liquid prepared at room temperature using purified water. The perm treatment was carried out on Japanese hair strands according to the perm treatment process published by Arimino, and the deodorizing effect on the unpleasant lingering odor of the hair and the texture of the hair after treatment were evaluated. The evaluation of the deodorizing effect on the unpleasant lingering odor of the hair was carried out according to the following criteria after towel drying (wet hair), after drying (dry hair), and the day after treatment. ◎◎: Has a pleasant scent with no unpleasant lingering odor ◎: No unpleasant lingering odor ○: There is a slight unpleasant odor, but it is within the acceptable range. △: Unpleasant lingering odor ×: Strong unpleasant lingering odor The texture of the hair was evaluated based on whether it felt smooth to the touch after treatment. Furthermore, when the second agent model solution was prepared, its appearance was visually inspected to evaluate whether or not there was any precipitation.

[0060] (Evaluation results) The results are shown in Table 4. As is clear from Table 4, when perming was performed using the second agent model solutions of Examples 8 to 14, which contained the slurry produced in Production Example 2 (copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone, with a content of 0.035 wt% in Examples 8, 10 to 14, and 0.14 wt% in Example 9), a deodorizing effect on the unpleasant lingering odor of hair after perming was achieved, and this effect persisted until the day after perming. The hair also had an excellent texture. This was thought to be due to the presence of polyvinylpyrrolidone on the surface, which reduced the surface roughness of the copper- and aluminum-doped mesoporous silica and reduced static electricity that could be generated between the silica and the hair. It is noteworthy that the persistence of the deodorizing effect on the unpleasant lingering odor of hair after perming was superior to that of Test Example 3, which used the first agent model solution containing the slurry produced in Production Example 2. By combining copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone with rose extract-containing powder, sugarcane extract-containing liquid, and herbal extract-containing liquid, which are known as odor-deodorizing and masking materials, an improved deodorizing effect was observed against unpleasant lingering odors in hair after treatment. Excellent results were obtained when performing a perm treatment using the second agent model solution of Example 10, which was combined with all of these materials. Furthermore, the second agent model solutions of Examples 8 to 14, which contained the slurry produced in Production Example 2, did not exhibit any precipitation during preparation, despite the inclusion of polyquaternium-11, because the copper- and aluminum-doped mesoporous silica contained in the slurry produced in Production Example 2 was surface-modified with polyvinylpyrrolidone. When performing a perm treatment using the second agent model solution of Comparative Example 5, which did not contain the slurry produced in Production Example 2, the slurry produced in Production Example 7, or a plant extract, no deodorizing effect against unpleasant lingering odors in hair after treatment was obtained.When a perm treatment was performed using the second agent model solution of Comparative Example 6, which contained the slurry produced in Production Example 7, a deodorizing effect on the unpleasant lingering odor of hair after the treatment was obtained, but the copper- and aluminum-doped mesoporous silica contained in the slurry produced in Production Example 7 was not surface-modified with polyvinylpyrrolidone, and therefore the texture of the hair was not excellent. Furthermore, when the second agent model solution was prepared, precipitation was observed. When a perm treatment was performed using the second agent model solution of Comparative Example 7, which contained a rose extract-containing powder instead of the slurry produced in Production Example 2, a deodorizing effect on the unpleasant lingering odor of hair after the treatment was observed, but the duration of the deodorizing effect did not reach the effect of a perm treatment using the second agent model solutions of Examples 8 to 14, which contained the slurry produced in Production Example 2. When a perm treatment was performed using the second agent model liquid of Comparative Example 8, which contained a sugarcane extract-containing liquid instead of the slurry produced in Production Example 2, the deodorizing effect on the unpleasant residual odor of hair after the treatment was inferior to the effect of a perm treatment using the second agent model liquids of Examples 8 to 14, which contained the slurry produced in Production Example 2, at all evaluation points.

[0061] [Table 4]

[0062] Test Example 5: Evaluation of the practicality of perm treatment agent (first agent) (Part 2) Thioglycolic acid, diethylenetriaminepentaacetic acid pentasodium solution, 28% ammonia water, polyquaternium-11, rose extract powder (Taiyo Fragrance's Rose Clean, which contains 10 wt% Gallica rose extract), sugarcane extract liquid (Mitsui Sugar's sugarcane extract MSX-245, which contains 0.02 wt%), herbal extract liquid (Ogawa Fragrance's mixed plant extract OG-D1, which contains 1.11 wt% of mixed plant extract (5 types of herbal medicines: Angelica sinensis, Peony, Cnidium Root, Rehmannia Root, and Ginger)), manufacturing Japanese hair strands were permed according to the perm treatment process published by Arimino using the slurry produced in Example 2, the slurry produced in Production Example 7, and purified water at room temperature. The first-component model solutions were prepared at room temperature using the compositions shown in Table 5. Second-component model solutions were prepared at room temperature using sodium bromate, pentasodium diethylenetriaminepentaacetate, 89% phosphoric acid, sodium hydroxide, and purified water. The deodorizing effect on the unpleasant lingering odor of the hair after perm treatment and the texture of the hair were evaluated using the same evaluation method as in Test Example 3. Furthermore, when the first-component model solutions were prepared, their appearance was visually inspected to evaluate the occurrence of precipitation. The results are shown in Table 5. As is clear from Table 5, even when thioglycolic acid was used as the reducing agent, the first-component model solution containing the slurry produced in Production Example 2 provided excellent deodorizing effect on the unpleasant lingering odor of the hair after perm treatment and texture, and no precipitation was observed when the first-component model solution was prepared.

[0063] [Table 5]

[0064] Test Example 6: Evaluation of the practicality of perm treatment agent (first agent) (Part 3) L-cysteine, thioglycolic acid, diethylenetriaminepentaacetic acid pentasodium solution, 28% ammonia water, polyquaternium-11, rose extract powder (Taiyo Fragrance's Rose Clean, which contains 10 wt% Gallica rose extract), sugarcane extract liquid (Mitsui Sugar Co., Ltd.'s sugarcane extract MSX-245, which contains 0.02 wt% sugarcane extract), herbal extract liquid (Ogawa Fragrance's mixed plant extract OG-D1, which contains 1.11 wt% of mixed plant extract (5 types of herbal medicines: Angelica sinensis, Peony, Cnidium Root, Rehmannia Root, and Ginger) extract) A Japanese hair bundle was permed according to the perm treatment process published by Arimino using first-agent model solutions of various compositions shown in Table 6, which were prepared at room temperature using the slurry produced in Production Example 2, the slurry produced in Production Example 7, and purified water. A second-agent model solution of the composition shown in Table 6, which was prepared at room temperature using sodium bromate, pentasodium diethylenetriaminepentaacetate solution, 89% phosphoric acid, sodium hydroxide, and purified water, was also used. The deodorizing effect on the unpleasant lingering odor of the hair after the treatment and the texture of the hair were evaluated using the same evaluation method as in Test Example 3. Furthermore, when the first-agent model solutions were prepared, their appearances were visually inspected to evaluate the occurrence of precipitation. The results are shown in Table 6. As is clear from Table 6, even when L-cysteine ​​and thioglycolic acid were used as reducing agents, the first-agent model solution containing the slurry produced in Production Example 2 provided excellent deodorizing effect on the unpleasant lingering odor of the hair after the treatment and texture of the hair, and it was confirmed that no precipitation was observed when the first-agent model solution was prepared.

[0065] [Table 6]

[0066] Test Example 7: Evaluation of the practicality of perm treatment agent (first agent) (Part 4) Thiolactic acid, diethylenetriaminepentaacetic acid pentasodium solution, 28% ammonia water, polyquaternium-11, rose extract-containing powder (Rose Clean from Taiyo Fragrance Co., Ltd., containing 10 wt% of Gallica rose extract), sugarcane extract-containing liquid (MSX-245 sugarcane extract from Mitsui Sugar Co., Ltd., containing 0.02 wt% of sugarcane extract), herbal extract-containing liquid (OG-D1 mixed plant extract from Ogawa Fragrance Co., Ltd., containing 1.11 wt% of mixed plant extract (five herbal medicines: Angelica sinensis, Peony root, Cnidium root, Rehmannia glutinosa, and Ginger)), Production Example 2 A Japanese hair bundle was permed according to the perm treatment process published by Arimino using the slurry produced in Example 2, the slurry produced in Production Example 7, and purified water at room temperature. The first-component model solutions were prepared at room temperature using the slurry produced in Production Example 6 and the slurry produced in Production Example 7. The first-component model solutions were prepared at room temperature using the slurry produced in Production Example 6 and the slurry produced in Production Example 7. The second-component model solutions were prepared at room temperature using the slurry produced in Production Example 6 and the slurry produced in Production Example 7. The second-component model solutions were prepared at room temperature using the slurry produced in Production Example 6 and the slurry produced in Production Example 7. The second-component model solutions were prepared at room temperature using the slurry produced in Production Example 6 and the slurry produced in Production Example 7. The second-component model solutions were prepared at room temperature using the slurry produced in Production Example 6 and the slurry produced in Production Example 7. The second-component model solutions were prepared at room temperature using the slurry produced in Production Example 6 and the slurry produced in Production Example 2. The second-component model solutions were prepared at room temperature using the slurry produced in Production Example 6 ...

[0067] [Table 7]

[0068] Test Example 8: Evaluation of the practicality of perm treatment agent (first agent) (Part 5) Butyrolactone thiol, diethylenetriaminepentaacetic acid pentasodium solution, sodium hydroxide, polyquaternium-11, rose extract powder (Taiyo Fragrance's Rose Clean, which contains 10 wt% of Gallica rose extract), sugarcane extract liquid (Mitsui Sugar Co., Ltd.'s sugarcane extract MSX-245, which contains 0.02 wt% of sugarcane extract), herbal extract liquid (Ogawa Fragrance's mixed plant extract OG-D1, which contains 1.11 wt% of mixed plant extract (5 types of herbal medicines: Angelica sinensis, Peony, Cnidium Root, Rehmannia Root, and Ginger)), A Japanese hair bundle was permed according to the perm treatment process published by Arimino using the slurry produced in Production Example 2, the slurry produced in Production Example 7, and purified water at room temperature. The first-component model solutions were prepared at room temperature using the slurry produced in Production Example 2, the slurry produced in Production Example 7, and purified water. The first-component model solutions were prepared at room temperature using the slurry produced in Production Example 2, and the second-component model solutions were prepared at room temperature using the slurry produced in Production Example 7 and the second-component model solutions were prepared at room temperature using the slurry produced in Production Example 2. The ... evaluated for their deodorizing effect on the unpleasant lingering odor of the hair after perm treatment and their texture using the same evaluation method as in Test Example 3. Furthermore, when the first-component model solutions were prepared, their appearance was visually inspected to evaluate the occurrence of precipitation. The results are shown in Table 8. As is clear from Table 8, even when butyrolactone thiol was used as the reducing agent, the first-component model solutions containing the slurry produced in Production Example 2 provided excellent deodorizing effect on the unpleasant lingering odor of the hair after perm treatment and their texture. No precipitation was observed when the first-component model solutions were prepared.

[0069] [Table 8]

[0070] Test Example 9: Evaluation of the practicality of perm treatment agent (second agent) (Part 2) The first agent model solution, which was prepared at room temperature using thioglycolic acid, diethylenetriaminepentaacetic acid pentasodium solution, 28% aqueous ammonia, and purified water, and which had the composition shown in Table 9, was used. The other agents included sodium bromate, diethylenetriaminepentaacetic acid pentasodium solution, 89% phosphoric acid, sodium hydroxide, polyquaternium-11, rose extract powder (Rose Clean from Taiyo Fragrance Co., Ltd., which contains 10 wt% of Gallica rose extract), sugarcane extract liquid (Mitsui Sugar Co., Ltd.'s sugarcane extract MSX-245, which contains 0.02 wt% of sugarcane extract), and raw materials. Using a medicinal extract-containing liquid (Ogawa Fragrance's mixed plant extract OG-D1, containing 1.11 wt% of mixed plant extract (five types of medicinal herbs: Angelica sinensis, Peony root, Cnidium root, Rehmannia glutinosa, and Ginger)), the slurry produced in Production Example 2, the slurry produced in Production Example 7, and second agent model solutions of various compositions shown in Table 9, prepared at room temperature using purified water, Japanese hair strands were permed according to the perm treatment process published by Arimino, and the deodorizing effect on the unpleasant residual odor of the hair after treatment and the texture were evaluated using the same evaluation method as used in Test Example 4. Furthermore, when the second agent model solutions were prepared, their appearance was visually inspected to evaluate the presence or absence of precipitation. The results are shown in Table 9. As is clear from Table 9, even when thioglycolic acid was used as the reducing agent, when a perm was performed using the second agent model solution containing the slurry produced in Production Example 2, it was confirmed that the perm had an excellent deodorizing effect on the unpleasant lingering odor of the hair after the treatment and had an excellent texture, and that no precipitation was observed when the second agent model solution was prepared.

[0071] [Table 9]

[0072] Test Example 10: Evaluation of the practicality of perm treatment agent (second agent) (Part 3) The first agent model solution, which was prepared at room temperature using L-cysteine, thioglycolic acid, pentasodium diethylenetriaminepentaacetate solution, 28% aqueous ammonia, and purified water, had the composition shown in Table 10; sodium bromate, pentasodium diethylenetriaminepentaacetate solution, 89% phosphoric acid, sodium hydroxide, polyquaternium-11, rose extract powder (Rose Clean from Taiyo Fragrance Co., Ltd., which contains 10 wt% Gallica rose extract), and sugarcane extract liquid (MSX-24 from Mitsui Sugar Co., Ltd., which contains 0.02 wt% sugarcane extract). 5), a liquid containing a herbal extract (Ogawa Fragrance Co., Ltd.'s mixed plant extract OG-D1, containing 1.11 wt% of a mixed plant extract (five herbal medicines: Angelica sinensis, Peony root, Cnidium root, Rehmannia glutinosa, and Ginger)), the slurry produced in Production Example 2, the slurry produced in Production Example 7, and second agent model solutions of various compositions shown in Table 10, prepared at room temperature using purified water, were used to perm strands of Japanese hair according to the perm treatment process published by Arimino, and the deodorizing effect on the unpleasant residual odor of the hair after treatment and the texture were evaluated using the same evaluation method as used in Test Example 4. Furthermore, when the second agent model solutions were prepared, their appearance was visually inspected to evaluate the presence or absence of precipitation. The results are shown in Table 10. As is clear from Table 10, even when L-cysteine ​​and thioglycolic acid were used as reducing agents, when a perm was performed using the second agent model solution containing the slurry produced in Production Example 2, it was confirmed that the perm had an excellent deodorizing effect on the unpleasant lingering odor of the hair after the treatment and had an excellent texture, and that no precipitation was observed when the second agent model solution was prepared.

[0073] [Table 10]

[0074] Test Example 11: Evaluation of the practicality of perm treatment agent (second agent) (Part 4) The first agent model solution, which was prepared at room temperature using thiolactic acid, diethylenetriaminepentaacetic acid pentasodium solution, 28% aqueous ammonia, and purified water, had the composition shown in Table 11; sodium bromate, diethylenetriaminepentaacetic acid pentasodium solution, 89% phosphoric acid, sodium hydroxide, polyquaternium-11, rose extract powder (Rose Clean from Taiyo Fragrance Co., Ltd., which contains 10 wt% of Gallica rose extract), sugarcane extract liquid (Mitsui Sugar Co., Ltd.'s sugarcane extract MSX-245, which contains 0.02 wt% of sugarcane extract), and herbal extract. Using a perm-containing liquid (Ogawa Fragrance Co.'s mixed plant extract OG-D1, containing 1.11 wt% of mixed plant extract (five types of medicinal herbs: Angelica sinensis, Peony root, Cnidium root, Rehmannia glutinosa, and Ginger)), the slurry produced in Production Example 2, the slurry produced in Production Example 7, and second agent model solutions of various compositions shown in Table 11, prepared at room temperature using purified water, Japanese hair strands were permed according to the perm treatment process published by Arimino, and the deodorizing effect on the unpleasant residual odor of the hair after treatment and the texture were evaluated using the same evaluation method as used in Test Example 4. Furthermore, when the second agent model solutions were prepared, their appearance was visually inspected to evaluate the presence or absence of precipitation. The results are shown in Table 11. As is clear from Table 11, even when thiolactic acid was used as the reducing agent, when a perm was performed using a second agent model solution containing the slurry produced in Production Example 2, it was confirmed that the perm had an excellent deodorizing effect on the unpleasant lingering odor of the hair after the treatment and had an excellent texture, and that no precipitation was observed when the second agent model solution was prepared.

[0075] [Table 11]

[0076] Test Example 12: Evaluation of the practicality of perm treatment agent (second agent) (Part 5) The first agent model solution having the composition shown in Table 12 was prepared at room temperature using butyrolactone thiol, pentasodium diethylenetriaminepentaacetic acid solution, sodium hydroxide, and purified water; sodium bromate, pentasodium diethylenetriaminepentaacetic acid solution, 89% phosphoric acid, sodium hydroxide, polyquaternium-11, rose extract-containing powder (Rose Clean from Taiyo Fragrance Co., Ltd., which contains 10 wt% Gallica rose extract); and sugarcane extract-containing liquid (MSX-245 sugarcane extract from Mitsui Sugar Co., Ltd., which contains 0.02 wt% sugarcane extract). Using a liquid containing a herbal extract (Ogawa Fragrance Co.'s mixed plant extract OG-D1, containing 1.11 wt% of mixed plant extract (five types of herbal medicines: Angelica sinensis, Peony root, Cnidium root, Rehmannia glutinosa, and Ginger)), the slurry produced in Production Example 2, the slurry produced in Production Example 7, and second agent model solutions of various compositions shown in Table 12, prepared at room temperature using purified water, Japanese hair strands were permed according to the perm treatment process published by Arimino, and the deodorizing effect on the unpleasant residual odor of the hair after treatment and the texture were evaluated using the same evaluation method as used in Test Example 4. Furthermore, when the second agent model solutions were prepared, their appearance was visually inspected to evaluate the presence or absence of precipitation. The results are shown in Table 12. As is clear from Table 12, even when butyrolactone thiol was used as the reducing agent, when a perm was performed using the second agent model solution containing the slurry produced in Production Example 2, it was confirmed that the perm had an excellent deodorizing effect on the unpleasant lingering odor of the hair after the treatment and had an excellent texture, and that no precipitation was observed when the second agent model solution was prepared.

[0077] [Table 12]

[0078] Test Example 13: Evaluation of the practicality of acid-heat treatment agents (Evaluation method) Glyoxyloyl carbocysteine, glyoxyloyl keratin amino acid, diethylenetriaminepentaacetic acid pentasodium solution, sodium hydroxide, polyquaternium-11, rose extract powder (Taiyo Fragrance's Rose Clean, which contains 10 wt% of Gallica rose extract), sugarcane extract liquid (Mitsui Sugar Co., Ltd.'s sugarcane extract MSX-245, which contains 0.02 wt% of sugarcane extract), herbal extract liquid (mixed plants (5 types of herbal medicines: Angelica sinensis, peony, Japanese hair strands were treated with an acid-heat treatment according to the acid-heat treatment process published by Arimino, using Ogawa Fragrance's mixed plant extract OG-D1) containing 1.11 wt% of extracts of Cnidium Root, Rehmannia Root, and Ginger, the slurry produced in Production Example 2, the slurry produced in Production Example 7, and model solutions of acid-heat treatment agents with various compositions shown in Table 13, which were prepared at room temperature using purified water. The treatment was evaluated for its deodorizing effect on the unpleasant lingering odor of the hair after treatment, and for its texture. The evaluation of the deodorizing effect on the unpleasant lingering odor of the hair was performed according to the following criteria after towel drying (wet hair), after drying and ironing (dry hair), and the day after treatment. ◎◎: Has a pleasant scent with no unpleasant lingering odor ◎: No unpleasant lingering odor ○: There is a slight unpleasant odor, but it is within the acceptable range. △: Unpleasant lingering odor ×: Strong unpleasant lingering odor The texture of the hair was evaluated based on whether it felt smooth to the touch after treatment.Furthermore, when the model acid-heat treatment liquid was prepared, its appearance was visually inspected to determine whether precipitation occurred.

[0079] (Evaluation results) The results are shown in Table 13. As is clear from Table 13, when acid-heat treatment was performed using the model solutions of acid-heat treatment agents of Examples 71 to 76, which contained the slurry produced in Production Example 2 (copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone, with a content of 0.035 wt% in Examples 71 and 73 to 76, and 0.14 wt% in Example 72), a deodorizing effect was obtained against the unpleasant lingering odor of hair after treatment, and this effect continued until the day after treatment. The hair also had an excellent texture. This is thought to be due to the presence of polyvinylpyrrolidone on the surface, which reduces the surface roughness of the copper- and aluminum-doped mesoporous silica and reduces static electricity that may occur between the hair and the surface. By combining copper- and aluminum-doped mesoporous silica surface-modified with polyvinylpyrrolidone with rose extract-containing powder, sugarcane extract-containing liquid, and herbal extract-containing liquid, which are known as odor-deodorizing and masking materials, an improved deodorizing effect on unpleasant residual odors in hair after treatment was observed, and excellent effects were obtained when acid-heat treatment treatment was performed using the acid-heat treatment model liquid of Example 73 combined with all of these materials. Furthermore, the acid-heat treatment model liquids of Examples 71 to 76, which contain the slurry produced in Production Example 2, doped with copper and aluminum mesoporous silica contained in the slurry produced in Production Example 2, were surface-modified with polyvinylpyrrolidone, so no precipitation was observed when prepared, despite the inclusion of polyquaternium-11. When an acid-heat treatment was performed using the model acid-heat treatment agent solution of Comparative Example 41, which did not contain the slurry produced in Production Example 2, the slurry produced in Production Example 7, or any plant extract, no deodorizing effect was obtained on the unpleasant lingering odor of the hair after the treatment.When an acid-heat treatment was performed using the model acid-heat treatment agent solution of Comparative Example 42, which contained the slurry produced in Production Example 7, a deodorizing effect on the unpleasant lingering odor of the hair after the treatment was obtained, but the copper- and aluminum-doped mesoporous silica contained in the slurry produced in Production Example 7 was not surface-modified with polyvinylpyrrolidone, and therefore the texture of the hair was not excellent.Furthermore, when a model acid-heat treatment liquid was prepared, precipitation was observed. When an acid-heat treatment treatment was performed using the model acid-heat treatment liquid of Comparative Example 43, which contained a sugarcane extract-containing liquid instead of the slurry produced in Production Example 2, when an acid-heat treatment treatment was performed using the model acid-heat treatment liquid of Comparative Example 44, which contained a liquid containing a herbal extract, or when an acid-heat treatment treatment treatment was performed using the model acid-heat treatment liquid of Comparative Example 45, which contained a rose extract-containing powder and a liquid containing a herbal extract, the deodorizing effect on unpleasant residual odors on hair after treatment was inferior at all evaluation points to the effect of an acid-heat treatment treatment using the model acid-heat treatment liquids of Examples 71 to 76, which contained the slurry produced in Production Example 2.

[0080] [Table 13]

[0081] Test Example 14: Evaluation of the practicality of shampoo (Part 1) The slurry produced in Production Example 1 was added to Sherpa Design Supplement Shampoo D-1, a shampoo from Arimino, at room temperature, and copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was blended to a content of 0.025 wt% (no precipitation was observed due to blending). Sherpa Design Supplement Shampoo D-1, which contains copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was applied to hair treated with various commercially available perm treatments or acid heat treatments according to the Sherpa Design Supplement Shampoo D-1 usage method recommended by Arimino. In all cases, the hair had no unpleasant odor after treatment and the texture of the hair was excellent.

[0082] Test Example 15: Evaluation of the practicality of shampoo (Part 2) The slurry produced in Production Example 1 was added to Arimino's Quolin Slim Balancer Shampoo at room temperature, and copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was blended to a content of 0.025 wt% (no precipitation was observed due to blending). Arimino's recommended method of using Quolin Slim Balancer Shampoo, which contains copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was used on hair that had been treated with various commercially available perm treatments or acid heat treatments. In all cases, the hair had no unpleasant odor after treatment and had excellent texture.

[0083] Test Example 16: Evaluation of the practicality of treatment agents The slurry produced in Production Example 1 was added to Arimino's treatment agent, Quolin Slim Balancer Treatment, at room temperature, and copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was blended to a content of 0.025 wt% (no precipitation was observed due to blending). Quolin Slim Balancer Treatment, which contains copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was applied to hair that had been treated with various commercially available perm treatments or acid heat treatments, according to the method of use recommended by Arimino. In all cases, the hair had no unpleasant residual odor after treatment, and the texture of the hair was excellent.

[0084] Test Example 17: Evaluation of the practicality of styling products (Part 1) The slurry produced in Production Example 1 was added at room temperature to BS Styling Bouncy Base Water, a styling product from Arimino, and copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was blended to a content of 0.025 wt% (no precipitation was observed due to blending). BS Styling Bouncy Base Water, containing copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was applied to hair that had been treated with various commercially available perm treatments or acid heat treatments, according to the method of use recommended by Arimino. In all cases, the hair had no unpleasant lingering odor after treatment, and the texture of the hair was excellent.

[0085] Test Example 18: Evaluation of the practicality of styling products (Part 2) The slurry produced in Production Example 1 was added to Arimino's styling product, Peace Pro Design Series Curl Milk, at room temperature, and copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was blended to a content of 0.025 wt% (no precipitation was observed due to blending). When Peace Pro Design Series Curl Milk, which contains copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was used on hair treated with various commercially available perm treatments or acid heat treatments according to the Arimino-recommended Peace Pro Design Series Curl Milk usage method, no unpleasant lingering odor was detected in the hair after treatment, and the hair texture was excellent in all cases.

[0086] Test Example 19: Evaluation of practicality in salons (Part 1) (Evaluation method) The slurry produced in Production Example 1 was added at room temperature to Arimino's CosmeCurl After Lotion (a blend of rose extract, sugarcane extract, and herbal extract), and copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was blended to a content of 0.025 wt% (no precipitation was observed due to blending). A salon model's hair was divided into two halves. One half was treated with the first agent, followed by a second agent treatment with CosmeCurl After Lotion containing copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. The other half was treated with the first agent, followed by a second agent treatment with CosmeCurl After Lotion without copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. The first agent used was Cosmecurl H (reducing agent: cysteamine) from Arimino. The specific method of perm treatment followed the basic process for using Cosmecurl published by Arimino.

[0087] (Evaluation results) The sulfur-containing odor of cysteamine and its decomposition products was detected in the hair of those who underwent perm treatment using a CosmeCurl after-lotion that did not contain copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. In contrast, the sulfur-containing odor of cysteamine and its decomposition products was not detected in the hair of those who underwent perm treatment using a CosmeCurl after-lotion that contained copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. These results confirmed that the addition of copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate to the second agent has a deodorizing effect on the sulfur-containing odor of cysteamine and its decomposition products. Furthermore, the hair of those who underwent a perm treatment using a CosmeCurl afterlotion containing copper- and aluminum-doped mesoporous silica whose surface had been modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate was found to have an excellent texture and be easy to run your fingers through. This is thought to be due to the presence of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate on the surface, which reduces the surface roughness of the copper- and aluminum-doped mesoporous silica and reduces static electricity that can occur between the hair and the hair.

[0088] Test Example 20: Evaluation of practicality in salons (Part 2) (Evaluation method) The slurry produced in Preparation Example 1 was added to Arimino's second agent, Quolin OX (containing no rose extract, sugarcane extract, or herbal extracts), at room temperature, and copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, was blended at a content of 0.025 wt% (no precipitation was observed due to the blending). A salon model's head was divided into two halves. One half was treated with the first agent, followed by a second agent treatment with Quolin OX containing copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. The other half was treated with the first agent, followed by a second agent treatment with Quolin OX containing no copper- and aluminum-doped mesoporous silica, surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. The first agent used was Arimino's Quolin CA-T200 (reducing agent: cysteamine and thioglycolic acid). The specific method of perming followed the basic process using Quolin published by Arimino.

[0089] (Evaluation results) The sulfur-containing odors of cysteamine, thioglycolic acid, and their decomposition products were detected in the hair of those who underwent perm treatment using Quolin OX without the copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. In contrast, the sulfur-containing odors of cysteamine, thioglycolic acid, and their decomposition products were not detected in the hair of those who underwent perm treatment using Quolin OX with the copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. These results confirmed that the addition of copper- and aluminum-doped mesoporous silica surface-modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate to the second agent has a deodorizing effect on the sulfur-containing odors of cysteamine, thioglycolic acid, and their decomposition products. Furthermore, the hair of those who underwent a perm treatment using Quolin OX, which contains copper- and aluminum-doped mesoporous silica whose surface has been modified with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, had an excellent texture that allowed the fingers to easily run through it. This is thought to be due to the presence of the copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate on the surface, which reduces the surface roughness of the copper- and aluminum-doped mesoporous silica and reduces static electricity that can occur between the hair and the hair. [Industrial Applicability]

[0090] The present invention has industrial applicability in that it can provide a hair treatment agent that has an excellent deodorizing effect and texture on hair after a perm treatment or the like, and that contains copper-doped porous silica blended so that it is stably dispersed and maintained.

Claims

1. A hair treatment agent containing copper-doped porous silica whose surface is modified with a polymer containing at least one vinylpyrrolidone unit selected from a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate and polyvinylpyrrolidone.

2. 2. The hair treatment composition according to claim 1, wherein the porous silica is further doped with aluminum.

3. 3. The hair treatment according to claim 1, wherein the amount of copper-doped porous silica surface-modified with a polymer containing a vinylpyrrolidone unit is 0.01 to 5 wt %.

4. 4. The hair treatment agent according to claim 1, further comprising a plant extract.

5. 5. The hair treatment agent according to claim 1, which is any one of a perm treatment agent, an acid heat treatment agent, a shampoo, a treatment agent, and a styling agent.

6. A method for producing a hair treatment agent, comprising the step of adding a slurry obtained by suspending copper-doped porous silica, the porous silica being surface-modified with a polymer containing at least one vinylpyrrolidone unit selected from a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate and polyvinylpyrrolidone, in a dispersant at any point during the process of producing the hair treatment agent.

7. A method for perming or acid heat treatment using the hair treatment agent according to any one of claims 1 to 5.

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