Surface-modified zinc oxide particles, dispersions, cosmetics

Abstract

To provide surface-modified zinc oxide particles with excellent ultraviolet shielding properties.SOLUTION: In the surface-modified zinc oxide particles of the present invention, a particle surface of the zinc oxide particles is treated with a hydrolyzable surface treatment agent, a color difference, ΔE, before and after irradiation with simulated sunlight is 4.0 or less, and an amount of cyclopentasiloxane absorbed oil is 20 mL / 100 g or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to surface-modified zinc oxide particles, a dispersion, and a cosmetic. [Background technology]

[0002] Zinc oxide is known to have excellent ultraviolet shielding properties, high gas barrier properties, and high transparency. Therefore, particles made of zinc oxide (hereinafter referred to as "zinc oxide particles") are used as a material for forming various materials that have functions such as ultraviolet shielding and gas barrier properties, as well as transparency. Examples of such materials include ultraviolet shielding films, ultraviolet shielding glass, cosmetics, and gas barrier films.

[0003] For the above-mentioned various materials, methods for improving transparency include, for example, reducing the primary particle size of zinc oxide particles, which are the forming material. Various methods, such as thermal decomposition and gas phase methods, have been investigated for reducing the primary particle size of zinc oxide particles (see, for example, Patent Documents 1 and 2).

[0004] When zinc oxide particles are used in cosmetics, the surfaces of the zinc oxide particles are subjected to a surface treatment with a surface treatment agent in order to adapt the surfaces of the zinc oxide particles to the properties of the cosmetics and to suppress the catalytic activity of the zinc oxide particles. In the following description, zinc oxide particles that have been surface-treated with a surface treatment agent and have the surface treatment agent on their surfaces are referred to as surface-modified zinc oxide particles. Such surface-modified zinc oxide particles are blended directly into cosmetics, or in the form of a dispersion in which they are dispersed in a dispersion medium, and then blended into cosmetics.

[0005] When zinc oxide particles are blended into oil-based cosmetics or the oil phase of emulsions, zinc oxide particles that have been surface-treated with a silane coupling agent having an alkoxy group are used (see, for example, Patent Documents 3 and 4). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-284527 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-95519 [Patent Document 3] International Publication No. 2017 / 130632 [Patent Document 4] Japanese Patent Application Laid-Open No. 2007-51188 Summary of the Invention [Problem to be solved by the invention]

[0007] However, further improvement in the ultraviolet shielding properties of surface-modified zinc oxide particles has been desired.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide surface-modified zinc oxide particles having excellent UV-shielding properties, and to provide a dispersion and a cosmetic containing such surface-modified zinc oxide particles. [Means for solving the problem]

[0009] That is, the surface-modified zinc oxide particles of the present invention are zinc oxide particles whose particle surfaces have been treated with a hydrolyzable surface treatment agent, and have a color difference ΔE before and after irradiation with simulated sunlight of 4.0 or less and a cyclopentasiloxane oil absorption of 20 mL / 100 g or less.

[0010] The dispersion of the present invention contains the surface-modified zinc oxide particles and a dispersion medium.

[0011] The cosmetic of the present invention contains at least one selected from the group consisting of the surface-modified zinc oxide particles and the dispersion liquids described above, and a cosmetic base raw material. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide surface-modified zinc oxide particles having excellent ultraviolet shielding properties, and also to provide a dispersion and a cosmetic containing such surface-modified zinc oxide particles. DETAILED DESCRIPTION OF THE INVENTION

[0013] The surface-modified zinc oxide particles, dispersion liquid, and cosmetic preparation according to the present invention will be described below. It should be noted that the present embodiment is specifically described to provide a better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified. The present invention allows for changes, omissions, substitutions, additions, etc. to be made to the values, amounts, materials, types, times, temperatures, order, etc., within the scope of the gist of the invention.

[0014] [Surface-modified zinc oxide particles] The surface-modified zinc oxide particles of this embodiment are zinc oxide particles whose particle surfaces have been treated with a hydrolyzable surface treatment agent, and have a color difference ΔE before and after irradiation with simulated sunlight of 4.0 or less and a cyclopentasiloxane oil absorption of 20 mL / 100 g or less. The color difference ΔE is preferably 3.5 or less, more preferably 3.0 or less, even more preferably 2.5 or less, and particularly preferably 2.0 or less. The lower limit of the color difference ΔE is 0, but it may be 0.01, 0.05, or 0.1. The surface-modified zinc oxide particles of this embodiment have a color difference ΔE of 4.0 or less and an oil absorption of cyclopentasiloxane of 20 mL / 100 g or less, and therefore have excellent ultraviolet shielding properties.

[0015] In this embodiment, the color difference ΔE before and after irradiation with simulated sunlight refers to a value measured by the following measurement method.

[0016] 3 g of t-butyl methoxydibenzoylmethane, 3 g of polyhydroxystearic acid, and 94 g of tri(caprylic / capric acid)glyceryl are mixed to prepare a solution in which the t-butyl methoxydibenzoylmethane is completely dissolved. Next, 2.0 g of the obtained solution and 3.0 g of surface-modified zinc oxide particles are mixed in a kneader (manufactured by Thinky Corporation, model number: ARE-310) until homogeneous to obtain a mixed solution. Next, the resulting mixture is sandwiched between assembled quartz cells for spectrophotometers (manufactured by GL Sciences, model number: AB20-UV-05) so that the optical path length is 0.5 mm, to prepare an assembled cell. Next, the resulting assembled cell was set in an ultraviolet-visible-near-infrared spectrophotometer (manufactured by JASCO Corporation, model number: V-770), and the diffuse reflectance spectrum of the mixed solution was measured using an integrating sphere. From the measurement results, the L1 * , a1 * , b1 * Calculate. Next, a xenon lamp in a small light irradiation test device (manufactured by Iwasaki Electric Co., Ltd., model number: EYE SUN-CUBE Xenon) was used to measure the cumulative light intensity of 300 kJ / m 2 The assembled cell containing the mixed solution is irradiated with simulated sunlight of 1000 kJ / cm. After irradiation, the assembled cell was set back in the UV-Vis-NIR spectrophotometer, and the diffuse reflectance spectrum was measured in the same manner as above. From the measurement results, the L2 * , a2 * , b2 * Calculate. Then, the color difference ΔE=((L2 * -L1 * ) 2 +(a2 * -a1 * ) 2 +(b2 * -b1 * ) 2 ) 1 / 2 Calculate. In addition, L1 * , a1 * , b1 * , L2 * , a2 * , b2 * L* a * b * This is a value on the color coordinate system chromaticity diagram.

[0017] This measurement method is a test for evaluating the surface treatment state of the surface-modified zinc oxide particles of this embodiment using simulated sunlight. The light irradiation test device uses a xenon light source that approximates sunlight. Therefore, irradiation by a xenon lamp using this measurement device can be considered equivalent to exposure to actual sunlight. The integrated light dose of this measurement method is 300 kJ / m 2 The irradiation of simulated sunlight of 10 minutes can evaluate the effect of ultraviolet rays equivalent to that of exposure to actual sunlight for about 10 minutes. When the color difference ΔE of the surface-modified zinc oxide particles prepared in the examples was measured, the measurement results of the color difference ΔE did not change significantly between the case where the irradiation time was 10 minutes and the case where the irradiation time was 3 hours. Therefore, in this measurement method, the cumulative light amount of 300 kJ / m2, which can be considered to be the irradiation time by sunlight for about 10 minutes, was used. 2 was evaluated. The measurement method in this embodiment will be described. t-Butyl methoxydibenzoylmethane is an organic UV absorber commonly used in cosmetics for UV protection. Polyhydroxystearic acid is a dispersant, and in this measurement, it is added to uniformly mix the surface-modified zinc oxide particles and t-butyl methoxydibenzoylmethane in the solvent. Caprylic / capric triglyceride is a common solvent used in cosmetics.

[0018] When the above mixture containing surface-modified zinc oxide particles and t-butyl methoxydibenzoylmethane is exposed to simulated sunlight, if the surface treatment is insufficient, the photocatalytic activity of the zinc oxide particles and the elution of zinc ions will alter the t-butyl methoxydibenzoylmethane, causing the mixture to discolor.

[0019] In this embodiment, the oil absorption refers to a value measured in accordance with JIS K6217-4 (method for determining oil absorption) using an absorption measuring device S-500 manufactured by Asahi Research Institute, Ltd. In this embodiment, 80 mL of surface-modified zinc oxide particles whose mass has been measured in advance are placed in the mixing chamber of the measuring device, and cyclopentasiloxane is added dropwise at an oil supply rate of 4 mL / min while rotating the stirring blades at 100 rpm. The oil absorption is determined by dividing the amount of drop that results in a torque value of 70% of the maximum torque value by the mass of the surface-modified zinc oxide particles measured in advance. The oil absorption of the surface-modified zinc oxide particles of this embodiment is 20 mL / 100 g or less, preferably 18 mL / 100 g or less, more preferably 16 mL / 100 g or less, and even more preferably 15 mL / 100 g or less.

[0020] The oil absorption value tends to be proportional to the specific surface area of ​​the surface-modified zinc oxide particles. 2 / g or more 8m 2 When the oil absorption is less than 1 mL / 100 g, the oil absorption is preferably 1 mL / 100 g or more and 19 mL / 100 g or less, more preferably 2 mL / 100 g or more and 16 mL / 100 g or less, and even more preferably 3 mL / 100 g or more and 14 mL / 100 g or less. The specific surface area of ​​the surface-modified zinc oxide particles is 8m 2 / g or more 65m 2 / g or less, the oil absorption is preferably 1 mL / 100g or more and 20 mL / 100g or less, more preferably 3 mL / 100g or more and 18 mL / 100g or less, and even more preferably 5 mL / 100g or more and 16 mL / 100g or less.

[0021] The oil absorption capacity of untreated zinc oxide particles varies depending on the specific surface area of ​​the zinc oxide particles. 2 / g or more 8m 2 If the specific surface area is less than 8m / g, it is about 20mL / 100g to 30mL / 100g. 2 If the volume is above 50 mL / 100 g, it is usually above 50 mL / 100 g. Therefore, when the oil absorption of surface-modified zinc oxide particles is smaller than that of zinc oxide particles before surface treatment, it can be inferred that the surface treatment is uniform and dense.

[0022] The present inventors have found that the UV-shielding ability of surface-modified zinc oxide particles is improved by surface-treating zinc oxide particles so that the color difference ΔE is 4.0 or less and the oil absorption is 20 mL / 100 g, and have completed the present invention. Furthermore, the present inventors have found that surface-modified zinc oxide particles having the color difference ΔE of 4.0 or less and the oil absorption of 20 mL / 100 g or less can be obtained by previously hydrolyzing a hydrolyzable surface modifier and then surface-treating the particles.

[0023] In this embodiment, the reason why the UV-shielding ability of the surface-modified zinc oxide particles is improved when the color difference ΔE is 4.0 or less and the oil absorption is 20 mL / 100 g or less is unclear. The reason for the small color difference ΔE is presumably due to suppression of photocatalytic activity and zinc ion elution. Furthermore, the reason for the oil absorption being 20 mL / 100 g or less is presumably due to the uniform and dense surface modification of the zinc oxide particles. However, there is no method for directly measuring how the hydrolyzable surface modifier modifies the surface of the zinc oxide particles. Therefore, it is unclear how the pre-hydrolyzed surface modifier modifies the surface of the zinc oxide particles, resulting in the small color difference ΔE and the small oil absorption. It is presumed that this is due to the uniform and dense presence of the surface modifier on the surface of the zinc oxide particles, but this alone does not provide an explanation.

[0024] In this embodiment, the use of a pre-hydrolyzed surface treatment agent results in the color difference ΔE of 4.0 or less and the oil absorption of 20 mL / 100 g or less, thereby improving the UV-shielding properties of the surface-modified zinc oxide particles. This effect is presumably due to a complex interaction of numerous factors. Specifically, this effect is presumably due to a complex interaction of numerous factors, such as the shape, specific surface area, and particle size distribution of the zinc oxide particles, the degree of hydrolysis of the hydrolyzable surface treatment agent, the degree of adhesion of the hydrolyzable surface treatment agent to the zinc oxide particles, and the rate of adhesion of the hydrolyzable surface treatment agent to the zinc oxide particles. Therefore, it is considered virtually impossible to directly identify the characteristics of the surface-modified zinc oxide particles of this embodiment based on the surface condition of zinc oxide particles that have been surface-modified after pre-hydrolysis of the hydrolyzable surface treatment agent.

[0025] Therefore, the present inventors conducted various studies, focusing on the color difference ΔE and the oil absorption, and found that the ultraviolet-shielding ability of surface-modified zinc oxide particles can be improved by surface-treating zinc oxide particles with a pre-hydrolyzed surface treatment agent so that the color difference ΔE is 4.0 or less and the oil absorption is 20 mL / 100 g or less.

[0026] The surface-modified zinc oxide particles of this embodiment preferably have a low transmittance in the ultraviolet region. The ultraviolet wavelength region that the surface-modified zinc oxide particles can block is affected by the size of the surface-modified zinc oxide particles. Therefore, when the specific surface area of ​​the surface-modified zinc oxide particles is 1.5 m, the transmittance in the ultraviolet region is preferably low. 2 / g or more 8m 2 When the transmittance is less than 1 / g, the total light transmittance at a wavelength of 360 nm measured by the following measurement method is preferably 55% or less, more preferably 50% or less, and even more preferably 45% or less. The specific surface area of ​​the surface-modified zinc oxide particles is 8m 2 / g or more 50m 2 / g or less, the total light transmittance at a wavelength of 360 nm measured by the following measurement method is preferably 48% or less, more preferably 40% or less, and even more preferably 35% or less. By incorporating surface-modified zinc oxide particles that have a low total light transmittance in the ultraviolet region, such as a wavelength of 360 nm, i.e., the sum of the linear transmittance and the diffuse transmittance, it is possible to obtain a cosmetic product with excellent ultraviolet blocking properties. The lower limit of the total light transmittance at a wavelength of 360 nm may be 0%, 1%, 10%, or 20%.

[0027] The surface-modified zinc oxide particles of this embodiment preferably have a high linear transmittance at a wavelength of 550 nm measured by the following measurement method. The linear transmittance at a wavelength of 550 nm is affected by the size of the surface-modified zinc oxide particles. 2 / g or more 8m 2 When the transmittance is less than 1 / g, the total light transmittance at a wavelength of 550 nm measured by the following measurement method is preferably 50% or more, more preferably 55% or more, and even more preferably 60% or more. The specific surface area of ​​the surface-modified zinc oxide particles is 8m 2 / g or more 50m 2 / g or less, the linear transmittance at a wavelength of 550 nm measured by the following measurement method is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. By incorporating surface-modified zinc oxide particles with high in-line transmittance at a wavelength of 550 nm, it is possible to obtain a cosmetic preparation with excellent transparency. The upper limit of the in-line transmittance at a wavelength of 550 nm may be 100%, 99%, or 98%.

[0028] In this embodiment, the total light transmittance at a wavelength of 360 nm and the linear transmittance at a wavelength of 550 nm are measured by the following measurement method. A dispersion liquid is obtained by mixing 10 g of surface-modified zinc oxide particles, 88 g of cyclopentasiloxane (manufactured by Dow-Toray Industries, Inc., model number: DOWSIL SH245 Fluid), and 2 g of polyglyceryl-3 polydimethylsiloxyethyl dimethicone (manufactured by Shin-Etsu Chemical Co., Ltd., model number: KF-6106). Next, this mixture is dispersed using a homogenizer (manufactured by IKA, ULTRA-TURRAX (registered trademark) series: T25basic) at 9500 rpm for 5 minutes to obtain a dispersion for evaluation.

[0029] The resulting dispersion for evaluation is diluted with cyclopentasiloxane so that the concentration of the surface-modified zinc oxide particles becomes 0.005% by mass. The diluted solution is placed in a quartz cell with an optical path length of 10 mm, and the total light transmittance at 360 nm and the linear transmittance at 550 nm are measured using a UV-Vis-NIR spectrophotometer (manufactured by JASCO Corporation, model number: V-770).

[0030] The surface-modified zinc oxide particles of this embodiment preferably have a small particle size (d90) at a cumulative volume percentage of 90% in the particle size distribution. The d90 is affected by the size of the surface-modified zinc oxide particles. Therefore, when the specific surface area of ​​the surface-modified zinc oxide particles is 1.5 m, the particle size is preferably small. 2 / g or more 8m 2 / g, the particle size (d90) at a cumulative volume percentage of 90% in the particle size distribution measured by the following measurement method is preferably 2 μm or less, more preferably 1 μm or less, even more preferably 0.8 μm or less, and even more preferably 0.6 μm or less. The specific surface area of ​​the surface-modified zinc oxide particles is 8m 2 / g or more 65m 2 / g or less, the particle size (d90) at a cumulative volume percentage of 90% in the particle size distribution measured by the following measurement method is preferably 1 μm or less, more preferably 0.5 μm or less, even more preferably 0.4 μm or less, and particularly preferably 0.3 μm or less. By blending surface-modified zinc oxide particles having a d90 of 2 μm or less into cosmetics, cosmetics with excellent transparency and UV-shielding properties can be obtained. The lower limit of d90 may be 0.05 μm or 0.1 μm.

[0031] The d90 of the surface-modified zinc oxide particles of this embodiment means a value measured by the following measurement method. A dispersion liquid is obtained by mixing 10 g of surface-modified zinc oxide particles, 88 g of cyclopentasiloxane (manufactured by Dow-Toray Industries, Inc., model number: DOWSIL SH245 Fluid), and 2 g of polyglyceryl-3 polydimethylsiloxyethyl dimethicone (manufactured by Shin-Etsu Chemical Co., Ltd., model number: KF-6106). Next, this mixture is dispersed using a homogenizer (manufactured by IKA, ULTRA-TURRAX (registered trademark) series: T25basic) at 9500 rpm for 5 minutes to obtain a dispersion for evaluation.

[0032] The resulting dispersion for evaluation was diluted with cyclopentasiloxane so that the content of surface-modified zinc oxide particles was 0.1% by mass. Using this diluted solution, the particle size (d90) at a cumulative volume percentage of 90% of the particle size distribution was measured using a dynamic light scattering particle size distribution analyzer (Microtrac-Bell, model: NANOTRAC WAVE). The particle size (d10) at a cumulative volume percentage of 10% of the particle size distribution and the particle size (d50) at a cumulative volume percentage of 50% of the particle size distribution could also be measured.

[0033] The surface-modified zinc oxide particles of this embodiment have a specific surface area of ​​8 m 2 / g or more 65m 2 / g or less, the total light transmittance at a wavelength of 360 nm after an accelerated test in which the particles are exposed to an environment of 85°C and 95% RH for 48 hours is preferably 40% or less. 2 / g or more 8m 2 When the surface modi?ed Zinc oxide particle has a total light transmittance of 55% or less at a wavelength of 360 nm after an accelerated test in Which the particle is exposed to an environment of 85° C. and 95% RH for 48 hours, the total light transmittance is preferably 55% or less at a wavelength of 360 nm after the accelerated test. By incorporating surface modi?ed Zinc oxide particles having a loW total light transmittance at a wavelength of 360 nm after an accelerated test into a cosmetic, it is possible to obtain a cosmetic having excellent stability over time. The lower limit of the total light transmittance at a wavelength of 360 nm after the accelerated test may be 0%, 1%, 10%, or 20%. The surface-modified zinc oxide particles of this embodiment preferably have a difference of 10% or less between the total light transmittance at a wavelength of 360 nm after 48 hours of exposure to an environment at 85°C and 95% RH and the total light transmittance at a wavelength of 360 nm before 48 hours of exposure to an environment at 85°C and 95% RH. The difference in total light transmittance is more preferably 8% or less, even more preferably 5% or less, and even more preferably 4% or less. The difference in total light transmittance means the value obtained by subtracting the value of the total light transmittance at a wavelength of 360 nm before the exposure from the value of the total light transmittance at a wavelength of 360 nm after the exposure. Conventional surface-modified zinc oxide particles have a problem in that their ultraviolet-shielding ability decreases over time when stored. However, the surface-modified zinc oxide particles of the present embodiment, in which the difference in total light transmittance is 10% or less, are prevented from decreasing in ultraviolet-shielding ability even when stored for a long period of time, and therefore have excellent stability over time. The lower limit of the difference in the total light transmittance is not particularly limited, and may be 0%, 0.1%, or 0.3%.

[0034] The surface-modified zinc oxide particles of this embodiment have a specific surface area of ​​8 m 2 / g or more 65m 2 / g or less, it is preferable that the linear transmittance at a wavelength of 550 nm after an accelerated test in which the film is exposed to an environment of 85°C and 95% RH for 48 hours is 90% or more. The surface-modified zinc oxide particles of this embodiment have a specific surface area of ​​1.5 m 2 / g or more 8m 2 When the transmittance is less than 1 / g, it is preferable that the linear transmittance at a wavelength of 550 nm after an accelerated test in which the film is exposed to an environment of 85° C. and 95% RH for 48 hours is 50% or more. By incorporating surface-modified zinc oxide particles that have a high linear transmittance at a wavelength of 550 nm after an accelerated test into a cosmetic, it is possible to obtain a cosmetic that has excellent stability over time. The upper limit of the in-line transmittance at a wavelength of 550 nm after the accelerated test may be 100%, 99%, or 98%.

[0035] The surface-modified zinc oxide particles of this embodiment have a specific surface area of ​​8 m 2 / g or more 65m 2 / g or less, it is preferable that the d90 after an accelerated test in which the particle size is exposed to an environment of 85°C and 95% RH for 48 hours is 0.3 µm or less. The surface-modified zinc oxide particles of this embodiment have a specific surface area of ​​1.5 m 2 / g or more 8m 2 When the d90 is less than 1 / g, the d90 after an accelerated test in which the particle size is exposed to an environment of 85°C and 95% RH for 48 hours is preferably 2 μm or less, more preferably 1 μm or less, even more preferably 0.8 μm or less, and even more preferably 0.6 μm or less. By incorporating surface-modified zinc oxide particles with a small d90 value after an accelerated test into a cosmetic, it is possible to obtain a cosmetic that is stable over time. The lower limit of d90 may be 0.05 μm or 0.1 μm.

[0036] The specific surface area of ​​the surface-modified zinc oxide particles of this embodiment can be selected arbitrarily, but is preferably 1.5 m 2 / g or more, and 2.5m 2 / g or more is more preferable, and 4m 2 The specific surface area of ​​the surface-modified zinc oxide particles is preferably 65 m / g or more. 2 / g or less, and 2 / g or less, and 2 / g or less is more preferable, and 45m 2 Optionally, the specific surface area of ​​the surface-modified zinc oxide particles is 40 m / g or less. 2 / g or less, and 2 / g or less, and 2 The above upper and lower limits of the specific surface area of ​​the surface-modified zinc oxide particles can be combined in any manner. The specific surface area of ​​the surface-modified zinc oxide particles is 1.5m 2 / g or more 65m 2 / g or less, the transparency and ultraviolet shielding properties are excellent when blended in cosmetics.

[0037] To increase the transparency of cosmetics, the specific surface area of ​​the surface-modified zinc oxide particles should be 8m 2 / g or more, and 15m 2 / g or more is more preferable, and 20m 2 It is more preferable that the saturation coefficient is 1 / g or more. For example, the specific surface area of ​​surface-modified zinc oxide particles is 20 m 2 / g or more 50m 2 / g or less, and 2 / g or more 48m 2 / g or less is more preferable, and 20m 2 / g or more 46m 2 / g or less is more preferable. 2 / g or more 30.0m 2 / g or less, 20.0m 2 / g or more 38.0m 2 / g or less, 20.0m 2 / g or more 44.0m 2 / g or less. When the specific surface area of ​​the surface-modified zinc oxide particles is equal to or greater than the above lower limit, a cosmetic having excellent transparency can be obtained when the particles are blended into a cosmetic. On the other hand, when the specific surface area of ​​the surface-modified zinc oxide particles is equal to or less than the above upper limit, the surface energy of the particles is not too high, and the particles can be blended into a cosmetic with less energy.

[0038] On the other hand, if you want to increase the UVA region ultraviolet ray blocking ability when blended into cosmetics, the specific surface area of ​​the surface-modified zinc oxide particles should be 20m 2 / g, and preferably less than 15m 2 / g, more preferably less than 8m 2 It is more preferable that the SiO2 content is less than 1 / g. For example, the specific surface area of ​​surface-modified zinc oxide particles is 1.5 m2 / g or more 20m 2 / g, and preferably less than 1.5m 2 / g or more 15m 2 More preferably, it is less than 1.5m 2 / g or more 8m 2 / g. When the specific surface area of ​​the surface-modified zinc oxide particles is equal to or greater than the above lower limit, a transparent cosmetic can be obtained when the particles are blended into a cosmetic. On the other hand, when the specific surface area of ​​the surface-modified zinc oxide particles is less than the above upper limit, the surface energy of the particles is not too high, so that the particles can be blended into a cosmetic with less energy, and a cosmetic with excellent ultraviolet ray blocking properties in the UVA region can be obtained.

[0039] The specific surface area (unit: m) of the surface-modified zinc oxide particles in this embodiment 2 / g) refers to the BET specific surface area determined by the BET method. The specific surface area of ​​the surface-modified zinc oxide particles can be measured by, for example, the BET method using a fully automatic specific surface area measuring device (trade name: Macsorb HM Model-1201, manufactured by Mountec Co., Ltd.).

[0040] In this embodiment, "treated with a surface treatment agent" means that the surface treatment agent comes into contact with or bonds to the zinc oxide particles through an interaction between them. Examples of the contact include physical adsorption. Examples of the bond include ionic bonding, hydrogen bonding, and covalent bonding.

[0041] The amount of the surface treatment agent in the surface-modified zinc oxide particles may be adjusted appropriately depending on the specific surface area of ​​the zinc oxide particles and the hydrophobicity of the cosmetic to be blended in. For example, the amount of the surface treatment agent in the surface-modified zinc oxide particles is preferably from 1 to 20% by mass, more preferably from 5 to 18% by mass, and even more preferably from 8 to 16% by mass, of the total mass of the zinc oxide particles and the surface treatment agent. When the amount of the surface treatment agent is equal to or greater than the above-mentioned lower limit, the hydrophilic zinc oxide particles can be blended into an oil-based cosmetic. When the amount of the surface treatment agent is equal to or less than the above-mentioned upper limit, the ultraviolet-shielding properties of the zinc oxide particles when blended into the cosmetic can be fully exhibited.

[0042] Specific surface area is 1.5m 2 / g or more 8m 2 In surface-modified zinc oxide particles having a color difference ΔE of less than 1.2% by mass and an oil absorption of less than 1.2% by mass, the amount of the surface treatment agent is preferably 1.2% by mass or more and 8% by mass or less, and more preferably 1.5% by mass or more and 6% by mass or less, based on the total mass of the zinc oxide particles and the surface treatment agent, from the viewpoint of reducing the color difference ΔE and the oil absorption and improving the stability over time in surface-modified zinc oxide particles having a color difference ΔE of less than 1.2% by mass and an oil absorption ... Specific surface area is 8m 2 / g or more 65m 2 In terms of reducing the color difference ΔE and oil absorption and improving stability over time in surface-modified zinc oxide particles having a surface-modified zinc oxide particle diameter of 1000 to 10000 sq ft or less, the content of the surface treatment agent is preferably 4% by mass or more and 20% by mass or less, more preferably 6% by mass or more and 18% by mass or less, and even more preferably 8% by mass or more and 16% by mass or less, based on the total mass of the zinc oxide particles and the surface treatment agent.

[0043] When the surface treatment agent is a silane coupling agent, the content of the surface treatment agent in the surface-modified zinc oxide particles can be calculated, for example, by quantitatively analyzing the amount of Si in the surface-modified zinc oxide particles using an inductively coupled plasma optical emission spectrometer.

[0044] "Zinc oxide particles" The specific surface area of ​​the zinc oxide particles (before surface treatment) in this embodiment can be selected arbitrarily, but is preferably 1.5 m 2 / g or more, and 2.5m 2 / g or more is more preferable, and 4m 2 The specific surface area of ​​the zinc oxide particles is more preferably 65 m / g or more. 2 / g or less, and 2 / g or less. If necessary, the specific surface area of ​​the zinc oxide particles is 55 m2 / g or less, and 2 / g or less, and 2 / g or less. The specific surface area of ​​the zinc oxide particles before surface treatment and the specific surface area of ​​the surface-modified zinc oxide particles vary somewhat depending on how the silane coupling agent is attached, but do not change significantly. Therefore, in order to obtain surface-modified zinc oxide particles with a desired specific surface area, zinc oxide particles having the desired specific surface area may be used. That is, the surface-modified zinc oxide particles of this embodiment can preferably have a specific surface area that is similar to the preferred value and range of the zinc oxide particles described above.

[0045] L of zinc oxide particles before treatment * a * b * b in the color space chromaticity diagram * is preferably 10 or less. * When the surface-modified zinc oxide particles are used, the b * The b of the surface-modified zinc oxide particles can be 4.0 or more and 18 or less. * However, the b of zinc oxide particles before surface treatment * As a result, the yellowness can be suppressed to a level suitable for use in cosmetics. * The lower limit of is not particularly limited, and may be 0, 1.0, or 1.5.

[0046] "Hydrolyzable surface treatment agent" The hydrolyzable surface treatment agent in this embodiment is not particularly limited as long as it is hydrolyzable and can be used in cosmetics. In this embodiment, "hydrolyzable" includes not only the hydrolysis of alkoxy groups, but also the dealkalization of metal soaps and the dehydrogenation of SiH in silicones.

[0047] Examples of such surface treatment agents include at least one selected from the group consisting of silane compounds, silicone compounds, fatty acids, fatty acid soaps, fatty acid esters, and organic titanate compounds. A surfactant may also be used.

[0048] Examples of the silane compound used for the surface treatment include alkylsilanes and fluoroalkylsilanes. Examples of alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, and octyltriethoxysilane. Examples of the fluoroalkylsilane include trifluoromethylethyltrimethoxysilane and heptadecafluorodecyltrimethoxysilane. Among these silane compounds, alkylsilanes are preferred, and octyltriethoxysilane is particularly preferred. These silane compounds may be used alone or in combination of two or more.

[0049] Examples of silicone compounds include silicone oil, methicone, dimethicone, hydrogen dimethicone, triethoxysilylethyl polydimethylsiloxyethyl dimethicone, triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone, (acrylates / tridecyl acrylate / triethoxysilylpropyl methacrylate / dimethicone methacrylate) copolymer, and triethoxycaprylylsilane. Examples of silicone oils include methylhydrogenpolysiloxane, dimethylpolysiloxane, and methylphenylpolysiloxane. These silicone compounds may be used alone or in combination of two or more, and copolymers of these silicone compounds may also be used as the silicone compound.

[0050] Examples of fatty acids include palmitic acid, isostearic acid, stearic acid, lauric acid, myristic acid, behenic acid, oleic acid, rosin acid, and 12-hydroxystearic acid. Examples of fatty acid soaps include magnesium stearate, zinc stearate, aluminum stearate, calcium stearate, magnesium myristate, zinc myristate, aluminum distearate, aluminum dimyristate, and aluminum 12-hydroxystearate. Examples of fatty acid esters include dextrin fatty acid esters, cholesterol fatty acid esters, sucrose fatty acid esters, and starch fatty acid esters.

[0051] Examples of organic titanate compounds include isopropyl triisostearoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri(dodecyl)benzenesulfonyl titanate, neopentyl(diallyl)oxy-tri(dioctyl)phosphate titanate, and neopentyl(diallyl)oxy-trineododecanoyl titanate.

[0052] Of the above surface treatment agents, it is preferable to use a silane coupling agent having an alkoxy group.

[0053] "Silane coupling agent having an alkoxy group" The silane coupling agent having an alkoxy group can be selected arbitrarily, and preferred examples include silane coupling agents represented by the following general formula (1) that can be used in cosmetics. R 1 Si(OR 2 )3···(1) (R 1 is an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group, or a phenyl group, R 2 represents an alkyl group having 1 to 4 carbon atoms.

[0054] Such a silane coupling agent is preferably at least one selected from the group consisting of alkylalkoxysilanes, allylalkoxysilanes, polysiloxanes having alkyl groups on the side chains, and polysiloxanes having allyl groups on the side chains.

[0055] Examples of alkylalkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltrippropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrippropoxysilane, ethyltributoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltrippropoxysilane, n-propyltributoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltrippropoxysilane, isopropyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrippropoxysilane, phenyltributoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane (triethoxycaprylylsilane), and n-octadecyltrimethoxysilane.

[0056] Examples of the silane coupling agent that can be used include polymeric silane coupling agents that have a siloxane skeleton as the main chain and have alkoxy groups and acrylic groups within the molecular structure, such as dimethoxydiphenylsilane-triethoxycaprylylsilane crosspolymer, triethoxysilylethyl polydimethylsiloxyethyl dimethicone, and triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone.

[0057] As the silane coupling agent, for example, fluoroalkylalkoxysilanes such as trifluoropropyltrimethoxysilane, perfluorooctyltriethoxysilane, and tridecafluorooctyltriethoxysilane can be used.

[0058] These silane coupling agents may be used alone or in combination of two or more.

[0059] Among the above-mentioned silane coupling agents, silane coupling agents having an octyl group in the molecule are more preferred. Specifically, silane coupling agents that can be used with a wide range of polar oil phases, from natural oils and ester oils to silicone oils, are more preferred. As such silane coupling agents, at least one selected from the group consisting of n-octyltriethoxysilane, n-octyltrimethoxysilane, and dimethoxydiphenylsilane-triethoxycaprylylsilane crosspolymer is particularly preferred. These silane coupling agents may be used alone or in combination of two or more.

[0060] In the surface-modified zinc oxide particles of this embodiment, in addition to a silane coupling agent, the zinc oxide particles may be surface-treated using a surface treatment agent other than a silane coupling agent that is used in cosmetics, as long as the properties of the surface-modified zinc oxide particles are not impaired.

[0061] The surface-modified zinc oxide particles of this embodiment are surface-modified zinc oxide particles in which the particle surfaces of the zinc oxide particles have been treated with a hydrolyzable surface treatment agent, and have a color difference ΔE before and after irradiation with simulated sunlight of 4.0 or less and an oil absorption of 20 mL / 100 g or less, and therefore have excellent ultraviolet shielding properties.

[0062] "Method for producing surface-modified zinc oxide particles" The method for producing surface-modified zinc oxide particles of this embodiment is a method for producing the above-mentioned surface-modified zinc oxide particles by wet treatment, and includes a first step of mixing a surface treatment agent with water to prepare a hydrolyzed liquid, a second step of mixing the hydrolyzed liquid with zinc oxide particles to prepare a first mixture, a third step after the second step of adding the hydrolyzed liquid obtained in the first step to the first mixture obtained in the second step and mixing them to prepare a second mixture containing the first mixture and the hydrolyzed liquid, and a fourth step of drying the second mixture obtained in the third step. In this embodiment, the term "wet treatment" refers to a surface treatment performed in a state where the total amount of solvent in the mixture, including the solvent contained in the hydrolyzed liquid, is 40 mass % or more.

[0063] "First step of preparing hydrolyzed liquid" In this step, a hydrolyzed liquid is prepared by mixing the surface treatment agent with water. By using such a hydrolyzed liquid in which at least a portion of the surface treatment agent has been hydrolyzed in advance, surface-modified zinc oxide particles having a small color difference ΔE and a small oil absorption can be produced. Although it is common to hydrolyze a surface treatment agent in advance, the significantly reduced color difference ΔE and oil absorption of surface-modified zinc oxide particles surface-treated with a hydrolyzed surface treatment agent is a remarkable effect that is beyond the range of prediction by those skilled in the art.

[0064] The hydrolyzed liquid may be prepared by maintaining a mixture of the surface treatment agent and water at a constant temperature for a predetermined period of time, thereby further promoting the hydrolysis of the surface treatment agent. In this treatment, the temperature of the mixed solution is not particularly limited and can be changed appropriately depending on the type of surface treatment agent, but is preferably 5°C or higher and 65°C or lower, and more preferably 30°C or higher and 60°C or lower.

[0065] The retention time is not particularly limited, but is preferably from 10 minutes to 180 minutes, and more preferably from 30 minutes to 120 minutes. During retention of the mixed solution, the mixed solution may be appropriately stirred.

[0066] The surface treatment agent used in the first step can be the same as that described above, and therefore a description thereof will be omitted. The water is not particularly limited as long as it is water that is generally used in cosmetics, and pure water, ion-exchanged water, distilled water, purified water, ultrapure water, natural water, etc. can be used.

[0067] In this step, in order to control the hydrolysis reaction of the surface treatment agent, it is preferable to mix a solvent other than water. The solvent is not particularly limited as long as it does not excessively control the hydrolysis of the surface treatment agent, and for example, an alcohol-based solvent can be mixed.

[0068] Examples of alcohol-based solvents include branched or linear alcohol compounds having 1 to 4 carbon atoms, which can be used alone or in combination of two or more. The alcohol compound contained in the alcohol-based solvent may be any of primary alcohol, secondary alcohol, and tertiary alcohol. The alcohol compound contained in the alcohol-based solvent may be any of monohydric alcohol, dihydric alcohol, and trihydric alcohol. More specifically, examples of alcohol-based solvents include methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butyl alcohol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, methanediol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-butene-1,4-diol, 1,4-butynediol, glycerin, diethylene glycol, and 3-methoxy-1,2-propanediol. Among these alcohol solvents, ethanol and isopropyl alcohol are preferred from the viewpoints that the hydrolysis reaction can be easily controlled and that their inclusion in cosmetics has little effect.

[0069] In this step, a catalyst may be mixed in order to promote the hydrolysis reaction of the surface treatment agent. The catalyst may be either an acid or a base. The acid catalyzes the hydrolysis reaction of the surface treatment agent in the dispersion, while the base catalyzes the condensation reaction of the hydrolyzed surface treatment agent with the silanol groups on the particle surface.

[0070] Examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, etc., and organic acids such as acetic acid, citric acid, formic acid, etc. These acids may be used alone or in combination of two or more. Examples of the base include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, ammonia, amines, etc. These bases may be used alone or in combination of two or more.

[0071] The content of the surface treatment agent in the mixed liquid is not particularly limited, but is preferably from 20% by mass to 70% by mass, and more preferably from 30% by mass to 60% by mass.

[0072] The water content in the mixed liquid is not particularly limited, but is preferably, for example, 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, and even more preferably 5% by mass or more and 10% by mass or less.

[0073] The content of the solvent in the mixed solution is not particularly limited, but is preferably 20% by mass or more and 70% by mass or less, and more preferably 30% by mass or more and 60% by mass or less. This allows the content of the surface treatment agent in the hydrolysis solution to be sufficiently high, and also allows a sufficient amount of water to be contained in the mixed solution. As a result, the hydrolysis reaction of the surface treatment agent can proceed efficiently.

[0074] The content of the catalyst in the mixed solution is not particularly limited, but is preferably, for example, from 10 ppm to 1000 ppm, and more preferably from 20 ppm to 800 ppm, which can sufficiently promote the hydrolysis reaction of the surface treatment agent.

[0075] "Second step of preparing a first mixture" This step is a step in which the hydrolysis liquid, zinc oxide particles, and a solvent are mixed to prepare a first mixture, and the zinc oxide particles are surface-treated with a surface treatment agent in a wet manner. The mixing is preferably carried out using a disperser from the viewpoint of uniformly applying the surface treatment agent to the surfaces of the zinc oxide particles. Therefore, mixing using a disperser will be described in detail. The zinc oxide particles can be the same as those described above, and therefore a description thereof will be omitted.

[0076] In this step, the hydrolysis solution, the solvent, and the zinc oxide particles are placed in a disperser to form a mixed solution. These materials may be placed simultaneously or sequentially. The order in which these materials are placed is not particularly limited. After being placed in the disperser, the materials may be left as they are without stirring, or may be simply stirred. Alternatively, these materials may be mixed in advance before being placed in the disperser.

[0077] "solvent" The solvent is not particularly limited as long as it is miscible with the surface treatment agent. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol, esters such as ethyl acetate and butyl acetate, and n-hexane, toluene, and xylene. Among these solvents, alcohols are preferred because they are miscible with water, and among alcohols, ethanol is particularly preferred.

[0078] The content of the solvent in the mixed solution can be selected arbitrarily, but is preferably 40% by mass or more in order to suppress aggregation of zinc oxide particles. The upper limit of the solvent content is not particularly limited, but is preferably 95% by mass or less in terms of production efficiency.

[0079] The content of zinc oxide particles in the mixed solution can be selected arbitrarily, but from the viewpoint of both suppressing aggregation of zinc oxide particles and achieving production efficiency, it is preferably 1% by mass to 55% by mass, and more preferably 10% by mass to 50% by mass. The content may be 15% by mass to 45% by mass, 20% by mass to 40% by mass, or 25% by mass to 35% by mass, etc.

[0080] The mixing ratio of the hydrolysis solution to the zinc oxide particles is not particularly limited, but it is preferable to mix them together in the third step described below so that the surface treatment agent accounts for 1% by mass to 20% by mass of the total mass of the zinc oxide particles and the surface treatment agent, more preferably 5% by mass to 18% by mass, and even more preferably 8% by mass to 16% by mass.

[0081] "Dispersion machine" The dispersing machine is not particularly limited as long as it can impart to the mixed solution a dispersing energy sufficient to perform surface treatment while loosening the agglomeration of zinc oxide particles. Examples of such dispersing machines include colloid mills, roll mills, ultrasonic dispersers, high-pressure homogenizers, ultimaizers, rotary mills, planetary mills, bead mills, sand mills, etc. Examples of dispersing media used in dispersing machines that require a dispersing medium include granular materials having a predetermined hardness, such as zirconia, glass, alumina, titania, and silicon nitride.

[0082] In this step, the mixed solution is dispersed using a disperser with a predetermined amount of energy or more to obtain surface-modified zinc oxide particles. The energy applied to the mixture may be adjusted appropriately according to the size of the disperser. Therefore, the dispersion conditions may be selected appropriately. For example, when dispersion is performed using a mill, specifically a bead mill using a container with a capacity of about 1 L, it is preferable to perform the dispersion treatment at a rotation speed of 500 rpm or more for a time period of 1 hour to 10 hours. However, the conditions may be selected as needed and are not limited to the above conditions. Furthermore, when dispersion treatment is performed using a mill, specifically a bead mill using a container with a capacity of approximately 1 L, the dispersion energy imparted to the mixed solution is preferably, for example, 100 W·h / kg or more and 600 W·h / kg or less, although conditions can be selected as needed and are not limited to the above conditions. In addition, since the crushing force of the bead mill depends on the centrifugal force of the beads on the periphery of the disk or pin inside the mill, when the bead weight is the total weight of the beads inside the mill, the product (impulse) of the centrifugal force and the dispersion time is calculated as 0.5 × 10 6 N·s or more 100×10 6 It is preferable to carry out dispersion processing so that the density is N·s or less. In addition, the surface-modified zinc oxide particles * The dispersion treatment may be continued until the b of the zinc oxide particles is 4.0 or more and 18 or less. In this case, a small amount of zinc oxide particles is taken out during the dispersion treatment, and the b of the zinc oxide particles is measured using a spectrophotometer. * The progress of the dispersion process may be confirmed by measuring the

[0083] The temperature during the dispersing step using a disperser is not particularly limited, but is preferably, for example, 20°C or higher and 45°C or lower.

[0084] "Third step of preparing a second mixture" This step may or may not be carried out after the second step. In this step, the first mixture obtained in the second step is mixed with the hydrolyzed liquid to form a second mixture, thereby performing a surface treatment on the zinc oxide particles with a surface treatment agent. By carrying out the surface treatment twice, the surface treatment agent is more likely to adhere uniformly to the particle surfaces. The surface treatment step may be carried out three, four, or more times.

[0085] The mixing ratio of the hydrolysis solution to the zinc oxide particles is not particularly limited, but it is preferable to mix the surface treatment agent in an amount of 1% by mass to 20% by mass, including the second step, based on the total mass of the zinc oxide particles and the surface treatment agent, more preferably 5% by mass to 18% by mass, and even more preferably 8% by mass to 16% by mass. The mass ratio between the surface treatment agent mixed in the second step and the surface treatment agent mixed in the third step is not particularly limited, but is preferably 0.5:1 to 3:1. In the second and subsequent surface treatment steps, the purpose is to suppress the remaining hydrolyzable reactive groups, so it is preferable to use a low mixing ratio of the surface treatment agent and promote the surface treatment by heating or the like.

[0086] This step is carried out to prevent hydrolyzable reactive groups from remaining, and therefore it is preferable to mix while heating. That is, in the second step, the surface treatment agent is uniformly adhered to the surfaces of the zinc oxide particles, and in the third step, the surface treatment is further promoted. The heating temperature is not particularly limited as long as it is a temperature that promotes the surface treatment, and is preferably, for example, 40° C. or higher and 150° C. or lower. If necessary, the heating temperature may be 40° C. or higher and 80° C. or lower, or 60° C. to 100° C., etc.

[0087] "Fourth step of drying the second mixture" This step is carried out to remove any water or solvent remaining in the second mixture. In this step, drying is preferably carried out using a drying apparatus. Note that treatment to shorten the drying time, such as solid-liquid separation, may be performed before drying. The drying apparatus is not particularly limited, and examples thereof include a box dryer, vacuum dryer, vibration dryer, fluidized bed dryer, band dryer, evaporator, Nauta mixer, Henschel mixer, Ribocone, paddle dryer, spray dryer, slurry dryer, flash dryer, rotary dryer, etc. The drying temperature is not particularly limited as long as it is a temperature at which the solvent can be removed, and is preferably, for example, 50°C or higher and 200°C or lower. It may also be 60°C or higher and 150°C or lower, or 70°C or higher and 120°C or lower, etc.

[0088] "Crushing process" The dried surface-modified zinc oxide particles may be subjected to a crushing treatment using a crusher. Any crusher can be selected, and examples thereof include an atomizer, a hammer mill, a jet mill, an impeller mill, and a pin mill. The crushing step can suppress the rough feeling of the surface-modified zinc oxide particles when they are incorporated into a cosmetic product. In other words, the feel when the surface-modified zinc oxide particles are used in a cosmetic product can be improved.

[0089] The surface-modified zinc oxide particles of this embodiment can be produced by the above steps.

[0090] [Dispersion] The dispersion of the present embodiment contains the surface-modified zinc oxide particles of the present embodiment and a dispersion medium. The dispersion may be formed by preparing the surface-modified zinc oxide particles of the present embodiment and mixing them with the dispersion medium. The dispersion liquid of this embodiment may preferably contain a paste-like dispersion with high viscosity.

[0091] The dispersion medium is not particularly limited as long as it can disperse the surface-modified zinc oxide particles. When the surface-modified zinc oxide particles are used in cosmetics, the dispersion medium is not particularly limited as long as it can be formulated into cosmetics. Examples of the dispersion medium include linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and diphenylpolysiloxane; cyclic polysiloxanes such as octamethylcyclotetrasiloxane, cyclopentasiloxane, and dodecamethylcyclohexasiloxane; modified polysiloxanes such as amino-modified polysiloxanes, polyether-modified polysiloxanes, alkyl-modified polysiloxanes, and fluorine-modified polysiloxanes; liquid paraffin, squalane, isoparaffin, branched light paraffin, petrolatum, ceresin, dodecane, and isododecane. Hydrophobic dispersion media include hydrocarbon oils such as ethanol, tridecane, tetradecane, hexadecane, isohexadecane, and octadecane; ester oils such as isopropyl myristate, cetyl isooctanoate, glyceryl trioctanoate, tri(caprylic / capric acid)glyceryl, and C12-15 alkyl benzoate; higher fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid; and higher alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, octyldodecanol, and isostearyl alcohol.Also, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, octanol, and glycerin; esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and γ-butyrolactone; ethers such as diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; benzene, toluene, etc. aromatic hydrocarbons such as benzene, ethylbenzene, 1-phenylpropane, isopropylbenzene, n-butylbenzene, tert-butylbenzene, sec-butylbenzene, o-xylene, m-xylene or p-xylene, 2-ethyltoluene, 3-ethyltoluene or 4-ethyltoluene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; amides such as dimethylformamide, N,N-dimethylacetoacetamide, N-methylpyrrolidone; nitriles such as acetonitrile; and natural oils such as oleic acid, jojoba oil, olive oil, coconut oil, grapeseed oil, castor oil, rice bran oil, horse oil, and mink oil. These dispersion media may be used alone or in combination of two or more.

[0092] When the surface-modified zinc oxide particles are used for cosmetics, the dispersion medium preferably used is the chain polysiloxane, the cyclic polysiloxane, the modified polysiloxane, the hydrocarbon oil, the ester oil, the higher fatty acid, the higher alcohol, the natural oil, ethanol, glycerin, or the like. These dispersion media may be used alone or in combination of two or more.

[0093] The dispersion of the present embodiment may contain commonly used additives to the extent that the properties of the dispersion are not impaired.

[0094] Examples of additives include preservatives, dispersants, dispersing aids, stabilizers, water-soluble binders, thickeners, oil-soluble drugs, oil-soluble dyes, oil-soluble proteins, UV absorbers, and the like.

[0095] The particle size (d50) at which the cumulative volume percentage of the particle size distribution in the dispersion of this embodiment is 50% is arbitrarily selected. 2 / g or more 8m 2 When it is less than / g, it is preferably 1 μm or less, more preferably 0.8 μm or less, and even more preferably 0.6 μm or less. The specific surface area of ​​the surface-modified zinc oxide particles is 8m 2 / g or more 65m 2 / g or less, the particle size (d50) is preferably 300 nm or less (0.3 μm or less), more preferably 250 nm or less, and even more preferably 200 nm or less. The upper limit of the particle size (d50) may be 150 nm or less, or 100 nm or less.

[0096] The lower limit of the particle size (d50) is not particularly limited, and may be, for example, 20 nm or more, 40 nm or more, or 60 nm or more. The upper and lower limits of the particle size (d50) can be combined arbitrarily.

[0097] In addition, the particle size (d90) when the cumulative volume percentage of the particle size distribution in the dispersion of this embodiment is 90% is determined when the specific surface area of ​​the surface-modified zinc oxide particles is 1.5 m 2 / g or more 8m 2 When it is less than / g, it is preferably 2 μm or less, more preferably 1 μm or less, even more preferably 0.8 μm or less, and even more preferably 0.6 μm or less. The specific surface area of ​​the surface-modified zinc oxide particles is 8m 2 / g or more 65m 2 / g or less, the particle size (d90) is preferably 350 nm or less, more preferably 300 nm or less, and even more preferably 250 nm or less.

[0098] The lower limit of the particle size (d90) is not particularly limited, and may be, for example, 60 nm or more, 80 nm or more, or 100 nm or more. The upper and lower limits of the particle size (d90) can be combined arbitrarily.

[0099] When the d50 of the dispersion is 1 μm or less, the surface-modified zinc oxide particles are easily distributed uniformly when a cosmetic product prepared using the dispersion is applied to the skin, which improves the UV-shielding effect, and when the d90 of the dispersion is 2 μm or less, the transparency of the dispersion is high, which also improves the transparency of the cosmetic product prepared using the dispersion, which is also preferred.

[0100] That is, by ensuring that the d50 and d90 values ​​of the dispersion of this embodiment are within the above ranges, a dispersion having excellent transparency and excellent UV-shielding properties can be obtained. Furthermore, cosmetics prepared using this dispersion also have excellent transparency and UV-shielding properties.

[0101] The cumulative volume percentage of the particle size distribution in the dispersion of this embodiment can be measured, for example, by using a dynamic light scattering particle size distribution measuring device (manufactured by Microtrack Bell, model number: NANOTRAC WAVE).

[0102] The content of the surface-modified zinc oxide particles in the dispersion of this embodiment is adjusted appropriately depending on the desired properties of the dispersion.

[0103] When the dispersion of this embodiment is used in a cosmetic, the content of the surface-modified zinc oxide particles in the dispersion is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. The upper and lower limits of the content of the surface-modified zinc oxide particles in the dispersion can be combined in any desired manner.

[0104] When the content of the surface-modified zinc oxide particles in the dispersion is within the above range, the dispersion contains the surface-modified zinc oxide particles at a high concentration, which improves the degree of freedom in formulating cosmetics prepared using the dispersion and allows the viscosity of the dispersion to be adjusted to a range that makes it easy to handle.

[0105] The method for producing the dispersion of the present embodiment is not particularly limited, and examples thereof include a method in which the surface-modified zinc oxide particles of the present embodiment and a dispersion medium are mechanically dispersed using a known dispersion device.

[0106] The dispersing device can be selected as necessary, and examples of the dispersing device include a stirrer, a planetary mixer, a homomixer, an ultrasonic homogenizer, a sand mill, a ball mill, and a roll mill.

[0107] The dispersion of this embodiment can be used in cosmetics as well as paints and the like having ultraviolet blocking properties, gas permeation inhibiting properties, and the like.

[0108] The dispersion of the present embodiment contains the surface-modified zinc oxide particles of the present embodiment, and therefore has excellent ultraviolet shielding properties.

[0109] [Composition] The composition of the present embodiment contains the surface-modified zinc oxide particles of the present embodiment, a resin, and a dispersion medium. The surface-modified zinc oxide particles of the present embodiment may be prepared and mixed with the resin and the dispersion medium to prepare the composition.

[0110] The content of the surface-modified zinc oxide particles in the composition of this embodiment is adjusted appropriately depending on the intended properties of the composition. For example, the content of the surface-modified zinc oxide particles in the composition of this embodiment is preferably 10% by mass or more and 40% by mass or less, and more preferably 20% by mass or more and 30% by mass or less.

[0111] When the content of the surface-modified zinc oxide particles in the composition is within the above range, the surface-modified zinc oxide particles are contained in the composition at a high concentration, thereby enabling the properties of the surface-modified zinc oxide particles to be fully obtained and providing a composition in which the surface-modified zinc oxide particles are uniformly dispersed.

[0112] The dispersion medium is not particularly limited as long as it is one that is commonly used in industrial applications, and examples of the dispersion medium include alcohols such as methanol, ethanol, and propanol, methyl acetate, ethyl acetate, toluene, methyl ethyl ketone, and methyl isobutyl ketone.

[0113] The content of the dispersion medium in the composition of the present embodiment is not particularly limited and is adjusted appropriately depending on the desired properties of the composition.

[0114] The resin is not particularly limited as long as it is one that is commonly used in industrial applications, and examples of the resin include acrylic resin, epoxy resin, urethane resin, polyester resin, and silicone resin.

[0115] The content of the resin in the composition of the present embodiment is not particularly limited and is adjusted appropriately depending on the desired properties of the composition.

[0116] The composition of the present embodiment may contain commonly used additives to the extent that the properties of the composition are not impaired. Examples of the additives include a polymerization initiator, a dispersant, and a preservative.

[0117] The method for producing the composition of the present embodiment is not particularly limited, and examples thereof include a method in which the surface-modified zinc oxide particles of the present embodiment, a resin, and a dispersion medium are mechanically mixed using a known mixer.

[0118] Another method is to mechanically mix the dispersion and the resin using a known mixer.

[0119] Examples of the mixing device include a stirrer, a planetary mixer, a homomixer, and an ultrasonic homogenizer.

[0120] A coating film can be formed by applying the composition of the present embodiment to a plastic substrate such as a polyester film by a common coating method such as roll coating, flow coating, spray coating, screen printing, brush coating, dipping, etc. These coating films can be used as ultraviolet screening films or gas barrier films.

[0121] The composition of the present embodiment has excellent ultraviolet shielding properties because it contains the surface-modified zinc oxide particles of the present embodiment.

[0122] [Cosmetics] The cosmetic of the present embodiment contains at least one selected from the group consisting of the surface-modified zinc oxide particles of the present embodiment and the dispersion of the present embodiment, and a cosmetic base raw material.

[0123] Here, the cosmetic base raw materials refer to the raw materials that form the main body of the cosmetic product, and examples thereof include oil-based raw materials, water-based raw materials, surfactants, powder raw materials, etc. Examples of oily raw materials include fats and oils, higher fatty acids, higher alcohols, and ester oils. Examples of aqueous raw materials include purified water, alcohol, thickeners, and the like. Examples of powder raw materials include colored pigments, white pigments, pearlescent agents, extender pigments, and the like. In this embodiment, the cosmetic base raw material can preferably be an oil-based raw material, a powder raw material, or an oil-based raw material and a powder raw material, and more preferably an oil-based raw material.

[0124] The cosmetic of this embodiment may refer to a cosmetic in which the surface-modified zinc oxide particles are contained in an oil component (oil phase) during the manufacturing process or in the final form, such as an oil-based cosmetic, an emulsion-type cosmetic containing surface-modified zinc oxide particles in an oil phase, or a powder solid cosmetic prepared by mixing surface-modified zinc oxide particles with an oil agent and then removing the oil agent and molding the cosmetic. The emulsion-type cosmetic may be an O / W type emulsion or a W / O type emulsion. In other words, the cosmetic of this embodiment preferably contains at least one selected from the group consisting of the surface-modified zinc oxide particles of this embodiment and the dispersion of this embodiment in the oil component or oil phase.

[0125] The oil component used in the oil phase of oil-based cosmetics or emulsions is not particularly limited as long as it is one that is commonly used in cosmetics, such as silicone oil, oils and fats, higher fatty acids, higher alcohols, ester oils, and natural oils.

[0126] Furthermore, the cosmetic of this embodiment may contain the aqueous raw materials, surfactants, powder raw materials, etc., as long as the properties of the cosmetic are not impaired.

[0127] The cosmetic of the present embodiment can be obtained, for example, by blending the surface-modified zinc oxide particles or dispersion of the present embodiment with a cosmetic base such as emulsion, cream, sunscreen, foundation, lipstick, blush, or eye shadow in a conventional manner.

[0128] Furthermore, the cosmetic of the present embodiment can be obtained by blending the surface-modified zinc oxide particles of the present embodiment into an oil phase to form an O / W or W / O emulsion, and then blending the emulsion with the raw materials of the cosmetic.

[0129] The content of the surface-modified zinc oxide particles in the cosmetic of this embodiment is adjusted appropriately depending on the desired properties of the cosmetic. For example, the lower limit of the content of the surface-modified zinc oxide particles may be 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more. Furthermore, the upper limit of the content of the surface-modified zinc oxide particles may be 50% by mass or less, 40% by mass or less, or 30% by mass or less. The upper and lower limits of the content of the surface-modified zinc oxide particles in the cosmetic can be combined in any desired manner.

[0130] Hereinafter, a sunscreen cosmetic will be specifically described as an example of the cosmetic. In order to effectively block ultraviolet rays, particularly long-wavelength ultraviolet rays (UVA), and to obtain a good feel when used with little powdery or squeaky texture, the lower limit of the content of surface-modified zinc oxide particles in the sunscreen cosmetic is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more. Furthermore, the upper limit of the content of surface-modified zinc oxide particles in the sunscreen cosmetic may be 50% by mass or less, 40% by mass or less, or 30% by mass or less. The upper and lower limits of the content of surface-modified zinc oxide particles in the sunscreen cosmetic can be combined in any manner.

[0131] The sunscreen cosmetic may contain, as necessary, a hydrophobic dispersion medium, inorganic fine particles or inorganic pigments other than surface-modified zinc oxide particles, a hydrophilic dispersion medium, oils and fats, surfactants, moisturizers, thickeners, pH adjusters, nutrients, antioxidants, fragrances, preservatives, dispersants, antifoaming agents, colorants, cosmetic ingredients, polymeric substances, biologically derived ingredients, plant-derived ingredients, antibacterial agents, bactericides, antifungal agents, aqueous ingredients, oily ingredients, vitamins, emulsifiers, stabilizers, solubilizers, pearlescent agents, refatting substances, and the like.

[0132] Examples of hydrophobic dispersion media include hydrocarbon oils such as liquid paraffin, squalane, isoparaffin, branched light paraffin, petrolatum, and ceresin; ester oils such as isopropyl myristate, cetyl isooctanoate, and glyceryl trioctanoate; silicone oils such as decamethylcyclopentasiloxane, dimethylpolysiloxane, and methylphenylpolysiloxane; higher fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid; and higher alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, hexyldodecanol, and isostearyl alcohol.

[0133] Examples of inorganic fine particles and inorganic pigments other than surface-treated particles contained in cosmetics include calcium carbonate, calcium phosphate (apatite), magnesium carbonate, calcium silicate, magnesium silicate, aluminum silicate, kaolin, talc, titanium oxide, aluminum oxide, yellow iron oxide, γ-iron oxide, cobalt titanate, cobalt violet, and silicon oxide.

[0134] The sunscreen cosmetic may further contain at least one organic ultraviolet absorber. Cosmetics containing both surface-modified zinc oxide particles and an organic ultraviolet absorber are preferred because they have a booster effect that broadens the ultraviolet blocking range and enhances the ultraviolet blocking properties.

[0135] Examples of organic ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, benzoylmethane-based ultraviolet absorbers, benzoic acid-based ultraviolet absorbers, anthranilic acid-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, cinnamic acid-based ultraviolet absorbers, silicone-based cinnamic acid ultraviolet absorbers, and triazine-based ultraviolet absorbers.

[0136] Examples of benzotriazole-based ultraviolet absorbers include 2,2'-hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and 2-(2'-hydroxy-5'-methylphenylbenzotriazole).

[0137] Examples of benzoylmethane ultraviolet absorbers include dibenzalazine, dianisoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane, 1-(4'-isopropylphenyl)-3-phenylpropane-1,3-dione, and 5-(3,3'-dimethyl-2-norbornylidene)-3-pentan-2-one.

[0138] Examples of benzoic acid-based ultraviolet absorbers include para-aminobenzoic acid (PABA), PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, and N,N-dimethyl PABA methyl ester.

[0139] Examples of anthranilic acid-based ultraviolet absorbers include homomenthyl-N-acetylanthranilate.

[0140] Examples of salicylic acid-based ultraviolet absorbers include amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-2-propanol phenyl salicylate.

[0141] Examples of cinnamic acid-based ultraviolet absorbers include octyl methoxycinnamate (ethylhexyl methoxycinnamate), glyceryl di-paramethoxycinnamate-mono-2-ethylhexanoate, octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxycinnamate, and isopropyl-p-methyl cinnamate. Examples of such cinnamates include 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, and glyceryl mono-2-ethylhexanoyl-di-para-methoxycinnamate.

[0142] Examples of silicone-based cinnamic acid ultraviolet absorbers include [3-bis(trimethylsiloxy)methylsilyl-1-methylpropyl]-3,4,5-trimethoxycinnamate, [3-bis(trimethylsiloxy)methylsilyl-3-methylpropyl]-3,4,5-trimethoxycinnamate, [3-bis(trimethylsiloxy)methylsilylpropyl]-3,4,5-trimethoxycinnamate, [3-bis(trimethylsiloxy)methylsilylbutyl]-3,4,5-trimethoxycinnamate, [3-tris(trimethylsiloxy)silylbutyl]-3,4,5-trimethoxycinnamate, and [3-tris(trimethylsiloxy)silyl-1-methylpropyl]-3,4-dimethoxycinnamate. Examples of the triazine-based ultraviolet absorber include bisethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, methylenebisbenzotriazolyltetramethylbutylphenol, trisbiphenyl triazine, and diethylhexylbutamido triazone.

[0143] Examples of organic ultraviolet absorbers other than those mentioned above include 3-(4'-methylbenzylidene)-d,l-camphor, 3-benzylidene-d,l-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 5-(3,3'-dimethyl-2-norbornylidene)-3-pentan-2-one, silicone-modified ultraviolet absorbers, and fluorine-modified ultraviolet absorbers.

[0144] The cosmetic of the present embodiment contains the surface-modified zinc oxide particles of the present embodiment, and therefore has excellent ultraviolet blocking properties. [Example]

[0145] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0146] [Example 1] "Preparation of surface-modified zinc oxide particles" (First step of preparing hydrolyzed liquid) 40.0 g of octyltriethoxysilane (OTS) (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBE-3083), 8.0 g of pure water, 0.8 g of 0.1 mol / L hydrochloric acid, and 51.2 g of ethanol were mixed at 60°C for 90 minutes to obtain a hydrolyzed liquid.

[0147] (Second step of preparing a first mixture) The resulting hydrolyzed liquid (4 g) and a specific surface area of ​​36.4 m 2 25 g of zinc oxide particles (manufactured by Sumitomo Osaka Cement Co., Ltd.) having a molecular weight of 1 / g were mixed with 71 g of ethanol. Next, this mixture was dispersed using a bead mill under the following dispersion conditions: a rotation speed of 1300 rpm, a temperature of 20° C., and a dispersion time of 40 minutes. After the dispersion treatment, the beads were removed to obtain a first mixture.

[0148] (Third step of preparing a second mixture) 100 g of the obtained first mixture and 3.0 g of the above hydrolyzed liquid were mixed at 50° C. for 30 minutes to obtain a second mixture.

[0149] (Fourth step of drying the second mixture) The resulting second mixture was subjected to solid-liquid separation, dried at 100° C. for 3 hours, and pulverized in a jet mill to obtain the surface-modified zinc oxide particles of Example 1.

[0150] "Measurement of the specific surface area of ​​surface-modified zinc oxide particles" The specific surface area of ​​the surface-modified zinc oxide particles of Example 1 was measured using a fully automatic specific surface area measuring device (trade name: Macsorb HM Model-1201, manufactured by Mountec Co., Ltd.) The results are shown in Table 1.

[0151] "Measurement of color difference ΔE of surface-modified zinc oxide particles before and after irradiation with simulated sunlight" 3 g of t-butyl methoxydibenzoylmethane, 3 g of polyhydroxystearic acid, and 94 g of tri(caprylic / capric acid)glyceryl were mixed to prepare a solution in which t-butyl methoxydibenzoylmethane was completely dissolved. Next, 2.0 g of the resulting solution and 3.0 g of the surface-modified zinc oxide particles of Example 1 were mixed in a kneader (Thinky Corporation, model number: ARE-310) until homogeneous to obtain a mixed solution. Next, the resulting mixed solution was sandwiched between assembled quartz cells for spectrophotometers (manufactured by GL Sciences, model number: AB20-UV-05) so that the optical path length was 0.5 mm, to prepare an assembled cell. Next, the resulting assembled cell was set in an ultraviolet-visible-near-infrared spectrophotometer (manufactured by JASCO Corporation, model number: V-770), and the diffuse reflectance spectrum of the mixed solution was measured using an integrating sphere. From the measurement results, the L1 * , a1 * , b1 * was calculated.

[0152] Next, a xenon lamp in a small light irradiation test device (manufactured by Iwasaki Electric Co., Ltd., model number: EYE SUN-CUBE Xenon) was used to measure the cumulative light intensity of 300 kJ / m 2 The assembled cell containing the above mixed solution was irradiated with simulated sunlight of 1000 kJ / cm. The assembled cell after irradiation was set back in the UV-Vis-NIR spectrophotometer, and the diffuse reflectance spectrum was measured in the same way. From the measurement results, the L2 * , a2 * , b2 * was calculated. Then, the color difference ΔE=((L2 * -L1 * ) 2 +(a2 * -a1 * ) 2 +(b2 * -b1 * ) 2 ) 1 / 2 The results are shown in Table 1.

[0153] "Measurement of cyclopentasiloxane oil absorption of surface-modified zinc oxide particles" The oil absorption of the surface-modified zinc oxide particles of Example 1 was measured in accordance with JIS K6217-4 (method for determining oil absorption) using an absorption measuring device S-500 manufactured by Asahi Research Institute. 80 mL of the surface-modified zinc oxide particles of Example 1, the mass of which had been measured in advance, was placed in the mixing chamber of the measuring device, and cyclopentasiloxane was added dropwise at an oil supply rate of 4 mL / min while rotating the stirring blade at 100 rpm. The amount of addition that resulted in a torque value of 70% of the maximum torque value was measured. The oil absorption was calculated by dividing this amount of addition by the mass of the surface-modified zinc oxide particles of Example 1. The results are shown in Table 1.

[0154] "Preparation of dispersion liquid" A mixed solution was obtained by mixing 10 g of the surface-modified zinc oxide particles of Example 1, 88 g of cyclopentasiloxane (manufactured by Dow-Toray Industries, Inc., model number: DOWSIL SH245 Fluid), and 2 g of polyglyceryl-3 polydimethylsiloxyethyl dimethicone (manufactured by Shin-Etsu Chemical Co., Ltd., model number: KF-6106). Next, this mixture was subjected to a dispersion treatment at 9500 rpm for 5 minutes using a homogenizer (manufactured by IKA, ULTRA-TURRAX (registered trademark) series: T25basic), and the dispersion of Example 1 was obtained.

[0155] "Evaluation of dispersibility based on particle size distribution" The dispersion liquid of Example 1 was diluted with cyclopentasiloxane so that the content of the surface-modified zinc oxide particles was 0.1% by mass to prepare a measurement liquid. Using this measurement solution, a dynamic light scattering particle size distribution analyzer (Microtrac-Bell, model: NANOTRAC WAVE) was used to measure the particle size (d10) when the cumulative volume percentage of the particle size distribution was 10%, the particle size (d50) when the cumulative volume percentage of the particle size distribution was 50%, and the particle size (d90) when the cumulative volume percentage of the particle size distribution was 90%. The results are shown in Table 2.

[0156] "Evaluation of dispersion transparency and UV blocking properties" The dispersion liquid of Example 1 was diluted with cyclopentasiloxane so that the concentration of the surface-modified zinc oxide particles was 0.005% by mass. This diluted solution was placed in a quartz cell with an optical path length of 10 mm, and the total light transmittance (linear transmittance + diffuse transmittance) (%) at 360 nm and the linear transmittance (%) at 550 nm were measured using a UV-Vis-NIR spectrophotometer (manufactured by JASCO Corporation, model number: V-770). The results are shown in Table 2. A low transmittance at 360 nm indicates a high ultraviolet blocking property, and therefore a low transmittance at 360 nm is preferred. A high transmittance at 550 nm indicates high transparency, and therefore a high transmittance at 550 nm is preferred.

[0157] "Evaluation of the temporal stability of surface-modified zinc oxide particles" The surface-modified zinc oxide particles of Example 1 were placed in a porcelain evaporating dish, covered with a polyimide film, and exposed to an environment of 85°C and 95% RH for 48 hours. Using the surface-modified zinc oxide particles of Example 1 after exposure, a dispersion was prepared in the same manner as above. The particle size distribution, transparency, and UV-shielding ability of the resulting dispersion were measured in the same manner as above. The results are shown in Table 2.

[0158] [Example 2] In the second step of preparing the mixture of Example 1, a specific surface area of ​​36.4 m 2Instead of using zinc oxide particles with a specific surface area of ​​19.2 m / g, 2 Surface-modified zinc oxide particles of Example 2 were obtained in the same manner as in Example 1, except that 1.6 g of hydrolyzed liquid was used instead of 3 g of hydrolyzed liquid in the third step of preparing the second mixture of Example 1, and 2.4 g of hydrolyzed liquid and 72.6 g of ethanol were used instead of 4 g of hydrolyzed liquid and 71 g of ethanol, using zinc oxide particles (manufactured by Sumitomo Osaka Cement Co., Ltd.) of 1.6 g of hydrolyzed liquid instead of 3 g of hydrolyzed liquid in the third step of preparing the second mixture of Example 1.

[0159] The specific surface area, color difference ΔE, and oil absorption of the surface-modified zinc oxide particles of Example 2 were measured in the same manner as in Example 1. The results are shown in Table 1.

[0160] A dispersion of Example 2 was obtained in the same manner as in Example 1, except that the surface-modified zinc oxide particles of Example 2 were used instead of the surface-modified zinc oxide particles obtained in Example 1. The particle size distribution, transparency and UV-shielding property of the dispersion of Example 2 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0161] The surface-modified zinc oxide particles of Example 2 were exposed to an environment of 85°C and 95% RH for 48 hours in the same manner as in Example 1. After exposure, the surface-modified zinc oxide particles of Example 2 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0162] [Example 3] In the second step of preparing the mixture of Example 1, a specific surface area of ​​36.4 m 2 Instead of using zinc oxide particles with a specific surface area of ​​5.8 m / g, 2 Surface-modified zinc oxide particles of Example 3 were obtained in the same manner as in Example 1, except that 1.2 g of hydrolyzed liquid and 73.8 g of ethanol were used instead of 4 g of hydrolyzed liquid and 71 g of ethanol, and 0.8 g of hydrolyzed liquid was used instead of 3 g of hydrolyzed liquid in the third step of preparing the second mixture of Example 1.

[0163] The specific surface area, color difference ΔE, and oil absorption of the surface-modified zinc oxide particles of Example 3 were measured in the same manner as in Example 1. The results are shown in Table 1.

[0164] A dispersion of Example 3 was obtained in the same manner as in Example 1, except that the surface-modified zinc oxide particles of Example 3 were used instead of the surface-modified zinc oxide particles obtained in Example 1. The particle size distribution, transparency and UV-shielding property of the dispersion of Example 3 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0165] The surface-modified zinc oxide particles of Example 3 were exposed to an environment of 85°C and 95% RH for 48 hours in the same manner as in Example 1. After exposure, the surface-modified zinc oxide particles of Example 3 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0166] "Preparation of surface-modified zinc oxide particles" (First step of preparing hydrolyzed liquid) 168 g of octyltriethoxysilane (OTS) (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBE-3083), 33.6 g of pure water, 3.4 g of 0.1 mol / L hydrochloric acid, and 215 g of ethanol were mixed at 60°C for 60 minutes to obtain a hydrolyzed liquid.

[0167] (Second step of preparing a first mixture) 400 g of the obtained hydrolyzed liquid was mixed with 2.5 kg of zinc oxide particles (manufactured by Sumitomo Osaka Cement Co., Ltd.) having a specific surface area of ​​39.4 m2 / g, and 7.1 kg of ethanol. Next, this mixture was dispersed using a bead mill under the following dispersion conditions: rotation speed 1500 rpm, temperature 20°C, and dispersion time 40 minutes. After the dispersion treatment, the beads were removed to obtain a first mixture.

[0168] (Third step of preparing a second mixture) 10 kg of the obtained first mixture and 300 g of the above hydrolyzed liquid were mixed at 50° C. for 30 minutes to obtain a second mixture.

[0169] (Fourth step of drying the second mixture) The resulting second mixture was subjected to solid-liquid separation, dried at 100° C. for 3 hours, and pulverized in a jet mill to obtain surface-modified zinc oxide particles of Example 4.

[0170] The specific surface area, color difference ΔE, and oil absorption of the surface-modified zinc oxide particles of Example 4 were measured in the same manner as in Example 1. The results are shown in Table 1.

[0171] A dispersion of Example 4 was obtained in the same manner as in Example 1, except that the surface-modified zinc oxide particles of Example 4 were used instead of the surface-modified zinc oxide particles obtained in Example 1. The particle size distribution, transparency and UV-shielding property of the dispersion of Example 4 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0172] The surface-modified zinc oxide particles of Example 4 were exposed to an environment of 85°C and 95% RH for 48 hours in the same manner as in Example 1. After exposure, the surface-modified zinc oxide particles of Example 4 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0173] [Comparative Example 1] (Second step of preparing a first mixture) 7 g of the hydrolyzed liquid obtained in the first step of Example 1 and a granular material having a specific surface area of ​​38.7 m 2 25 g of zinc oxide particles (manufactured by Sumitomo Osaka Cement Co., Ltd.) with a molecular weight of 1 / g were mixed with 68 g of ethanol. Next, this mixture was dispersed using a bead mill under the following dispersion conditions: a rotation speed of 1300 rpm, a temperature of 20° C., and a dispersion time of 40 minutes. After the dispersion treatment, the beads were removed to obtain a first mixture.

[0174] (drying process) The obtained first mixture was subjected to solid-liquid separation and dried at 100° C. for 3 hours to obtain surface-modified zinc oxide particles of Comparative Example 1.

[0175] The specific surface area, color difference ΔE, and oil absorption of the surface-modified zinc oxide particles of Comparative Example 1 were measured in the same manner as in Example 1. The results are shown in Table 1.

[0176] A dispersion liquid of Comparative Example 1 was obtained in the same manner as in Example 1, except that the surface-modified zinc oxide particles of Comparative Example 1 were used instead of the surface-modified zinc oxide particles obtained in Example 1. The particle size distribution, transparency and ultraviolet shielding property of the dispersion of Comparative Example 1 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0177] The surface-modified zinc oxide particles of Comparative Example 1 were exposed to an environment of 85°C and 95% RH for 48 hours in the same manner as in Example 1. After exposure, the surface-modified zinc oxide particles of Comparative Example 1 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0178] Comparative Example 2 Specific surface area is 39.4m 2 100 g of zinc oxide particles (manufactured by Sumitomo Osaka Cement Co., Ltd.) with a mass of 1 / g was placed in a Henschel mixer. While stirring the zinc oxide particles in the Henschel mixer, a mixture of 6 g of octyltriethoxysilane (trade name: KBE-3083, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.45 g of pure water, and 8.55 g of isopropyl alcohol was added. This mixture was mixed in the Henschel mixer and stirred for 1 hour. The resulting mixture was then pulverized in a jet mill, and the pulverized powder was dried at 100° C. for 3 hours to obtain surface-modified zinc oxide particles of Comparative Example 2.

[0179] The specific surface area, color difference ΔE, and oil absorption of the surface-modified zinc oxide particles of Comparative Example 2 were measured in the same manner as in Example 1. The results are shown in Table 1.

[0180] A dispersion liquid of Comparative Example 2 was obtained in the same manner as in Example 1, except that the surface-modified zinc oxide particles of Comparative Example 2 were used instead of the surface-modified zinc oxide particles obtained in Example 1. The particle size distribution, transparency and UV-shielding property of the dispersion of Comparative Example 2 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0181] The surface-modified zinc oxide particles of Comparative Example 2 were exposed to an environment of 85°C and 95% RH for 48 hours in the same manner as in Example 1. After exposure, the surface-modified zinc oxide particles of Comparative Example 2 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0182] Comparative Example 3 Specific surface area is 39.4m 2Instead of using zinc oxide particles of 0.1g / g, 6g of octyltriethoxysilane, 0.45g of pure water, and 8.55g of isopropyl alcohol, a solution with a specific surface area of ​​5.8m 2 Surface-modified zinc oxide particles of Comparative Example 3 were obtained in the same manner as in Comparative Example 2, except that zinc oxide particles of 0.15 g / g, 2 g of octyltriethoxysilane, 0.15 g of pure water, and 5.0 g of isopropyl alcohol were used.

[0183] The specific surface area, color difference ΔE, and oil absorption of the surface-modified zinc oxide particles of Comparative Example 3 were measured in the same manner as in Example 1. The results are shown in Table 1.

[0184] A dispersion liquid of Comparative Example 3 was obtained in the same manner as in Example 1, except that the surface-modified zinc oxide particles of Comparative Example 3 were used instead of the surface-modified zinc oxide particles obtained in Example 1. The particle size distribution, transparency and UV-shielding property of the dispersion of Comparative Example 3 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0185] The surface-modified zinc oxide particles of Comparative Example 3 were exposed to an environment of 85°C and 95% RH for 48 hours in the same manner as in Example 1. After exposure, the surface-modified zinc oxide particles of Comparative Example 3 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0186] Comparative Example 4 Specific surface area 39.4m 2 / g zinc oxide particles (manufactured by Sumitomo Osaka Cement Co., Ltd.), i.e., zinc oxide particles that had not been surface-treated, were used as Comparative Example 4, and the color difference ΔE and oil absorption were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0187] [Table 1]

[0188] [Table 2]

[0189] The results in Tables 1 and 2 confirm that the surface-modified zinc oxide particles of Examples 1 to 3 have smaller color difference ΔE and oil absorption and are superior in UV blocking properties compared to the surface-modified zinc oxide particles of Comparative Examples 1 to 4. [Industrial Applicability]

[0190] The present invention can provide surface-modified zinc oxide particles having excellent ultraviolet shielding properties. The surface-modified zinc oxide particles of the present invention have excellent ultraviolet shielding properties and transparency equal to or greater than that of conventional particles, and therefore have great industrial value when used in cosmetics.

Claims

1. Surface-modified zinc oxide particles, the particle surfaces of which are treated with a hydrolyzable surface treatment agent, The color difference ΔE before and after irradiation with pseudo-sunlight is 4.0 or less, Surface-modified zinc oxide particles having a cyclopentasiloxane oil absorption of 20 mL / 100 g or less.

2. 2. The surface-modified zinc oxide particles according to claim 1, wherein the difference between the total light transmittance at a wavelength of 360 nm after 48 hours of exposure to an environment of 85°C and 95% RH and the total light transmittance at a wavelength of 360 nm before 48 hours of exposure to an environment of 85°C and 95% RH is 10% or less.

3. 3. The surface-modified zinc oxide particles according to claim 1, wherein the surface treatment agent is a hydrolyzed silane coupling agent having an alkoxy group.

4. A dispersion comprising the surface-modified zinc oxide particles according to any one of claims 1 to 3 and a dispersion medium.

5. A cosmetic comprising at least one selected from the group consisting of the surface-modified zinc oxide particles according to any one of claims 1 to 3 and the dispersion according to claim 4, and a cosmetic base raw material.

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