Spherical silica particle powder and method for producing spherical silica particle powder

Abstract

The present invention provides a novel material which is not limited to a nanomaterial, and which has excellent colorability and does not degrade electrical properties when used in electronic materials. A spherical silica particle powder of the present invention comprises a plurality of spherical element-loaded silica particles, which are particles in which at least one of the transition metal elements of the periodic table is supported on a spherical silica particle, and contains 0.01 to 40 mass% of the transition metal element in the spherical silica particle powder, and the L* value, a* value, and b* value in the L*a*b* colorimetric system standardized by CIE in the spherical silica particle powder satisfy √{(a* 2 +(b*) 2 +(100−L*) 2}≥20.

Description

Technical Field

[0001] This invention relates to spherical silica particle powder and a method for manufacturing spherical silica particle powder. Background Technology

[0002] Coloring resin compositions used in electronic materials and cosmetics have traditionally included coloring materials for coloring purposes, such as pigments and dyes including carbon black, titanium black, ferrous oxide, iron oxide and chromium oxide (III).

[0003] For example, as a coloring material for marking semiconductor chips in electronic materials, Patent Document 1 describes the use of non-conductive carbon, and Patent Document 2 describes the use of titanium black.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2004-156052

[0007] Patent Document 2: Japanese Patent Application Publication No. 4-72360 Summary of the Invention

[0008] The problem the invention aims to solve

[0009] On the other hand, the current situation is that pigments have problems with weather resistance and insulation, or there is a trend in the cosmetics industry to restrict materials that belong to nanomaterials, thus limiting the types of pigments that can be used. Pigments such as iron oxide also have problems such as having a distinctive odor or fading due to sweat.

[0010] Therefore, the objective of this invention is to provide a novel material with excellent colorability that is not limited by nanomaterials and does not reduce electrical properties when used in electronic materials.

[0011] Solution for solving the problem

[0012] The inventors conducted in-depth research and found that the above-mentioned problems could be solved by spherical silica particle powder containing spherical silica particles on which a specific metal element is loaded in a specific amount, thereby completing the present invention.

[0013] One aspect of the present invention relates to a spherical silica particle powder, comprising a plurality of spherical element-loaded silica particles, wherein the spherical element-loaded silica particles are particles on which at least one transition metal element from the periodic table is loaded, and the spherical silica particle powder contains 0.01 to 40% by mass of the transition metal element, and the spherical silica particle powder is CIE-standardized L * a * b * L in the colorimetric system * value, a * value and b * The value satisfies √{(a*)} 2 +(b*) 2 +(100-L*) 2 ≥20.

[0014] In addition, another aspect of the present invention relates to a method for manufacturing spherical silica particle powder, which includes: using a spherical silica precursor obtained by a wet process, loading the silica precursor with at least one of the transition metal elements of the periodic table.

[0015] In addition, another aspect of the present invention relates to a resin composition comprising 5 to 90% by mass of the above-mentioned spherical silica particle powder.

[0016] In addition, another aspect of the present invention relates to a slurry composition comprising 1 to 80% by mass of the above-mentioned spherical silica particles.

[0017] In addition, another aspect of the present invention relates to a cosmetic composition comprising the above-mentioned spherical silica particle powder.

[0018] The effects of the invention

[0019] According to the present invention, spherical silica particle powder exhibiting excellent hue can be provided. Silica, due to its low dielectric constant, displays good dielectric properties when used in electronic materials, and is not limited by nanomaterials. Therefore, the spherical silica particle powder of the present invention is suitable for use as an additive in coloring resin compositions used in electronic materials and the like, as well as in cosmetic compositions. Detailed Implementation

[0020] The present invention will now be described, but it is not limited to the examples described below. Furthermore, in this specification, the "~" sign indicating a numerical range refers to the inclusion of the values ​​before and after it as a lower limit and an upper limit.

[0021] In addition, in this specification, "spherical silica particle powder" refers to powder that is an aggregate of spherical silica particles.

[0022] In addition, in this instruction manual, "mass" and "weight" have the same meaning.

[0023] The spherical silica particle powder of the present invention (hereinafter referred to as "this embodiment") comprises a plurality of spherical silica particles loaded with elements. The spherical silica particles loaded with elements are particles on which at least one transition metal element from the periodic table is loaded. The spherical silica particle powder contains 0.01 to 40% by mass of the transition metal element. The L-type of the spherical silica particle powder is standardized by CIE. * a * b * L in the colorimetric system * value, a * value and b * The value satisfies √{(a*)} 2 +(b*) 2 +(100-L*) 2 ≥20.

[0024] In recent years, there has been a growing demand for lower dielectric constants and lower dielectric loss tangents in resin compositions for semiconductor sealing. This is particularly problematic when using conductive materials such as carbon black as coloring agents, as it leads to a deterioration in the dielectric loss tangent. Furthermore, when using titanium black as a coloring agent, if its proportion relative to the overall semiconductor sealing resin composition is not higher than that of carbon black, there is a tendency for reduced colorability, opacity, and laser marking properties. However, if a large amount of titanium black is blended in to avoid this problem, electrical properties such as volume resistivity decrease.

[0025] In contrast, silicon dioxide (SiO2) has a small dielectric constant (3.9) and a small thermal expansion coefficient (3~7.9ppm / ℃). In this invention, it was discovered that by loading transition metal elements onto silicon dioxide, silicon dioxide can be colored itself, thus producing colored spherical silicon dioxide particle powder.

[0026] By setting the content of transition metal elements in spherical silica particles to 0.01~40% by mass, L * value, a * value and b * The value satisfies √{(a * ) 2 +(b * ) 2 +(100-L * ) 2A hue with a value ≥20 that is sufficiently visually recognizable, and a powder with a low dielectric constant and a low dielectric loss tangent. * This indicates brightness; the closer the value is to 0, the closer it is to white, and the larger the value is, the closer it is to black (deviating from the natural color of the silicon dioxide particles, i.e., white).

[0027] √{(a * ) 2 +(b * ) 2 +(100-L * ) 2 The value} represents the intensity of the hue. When the value is above 20, the hue of the spherical silica particles changes from the white of silica itself to different degrees of color intensity that can be clearly distinguished.

[0028] √{(a * ) 2 +(b * ) 2 +(100-L * ) 2 The value of} is preferably 25 or higher, more preferably 30 or higher, further preferably 40 or higher, particularly preferably 60 or higher, and most preferably 75 or higher. Furthermore, from the viewpoint of ease of hue adjustment, √{(a * ) 2 +(b * ) 2 +(100-L * ) 2 The value of} is preferably 90 or less, more preferably 85 or less, and even more preferably 80 or less. That is, √{(a * ) 2 +(b * ) 2 +(100-L * ) 2 The value of} is preferably in the range of 20 to 90 (20 ≤ √{(a * ) 2 +(b * ) 2 +(100-L * ) 2}≤90).

[0029] L of spherical silica particles * value, a * value and b * The values ​​were measured using a spectrophotometer (e.g., the "SE-7700" manufactured by Nippon Denshoku Kogyo Co., Ltd.) to measure the powder that was filled into a glass bath and tapped about 30 times to form a smooth pressed powder.

[0030] Transition metals are elements belonging to groups 3 through 11 of the periodic table. Examples of group 3 metals include scandium (Sc), yttrium (Y), and the lanthanides (lanthanum (La), cerium (Ce), etc.). Examples of group 4 metals include titanium (Ti) and zirconium (Zr). Examples of group 5 metals include vanadium (V) and niobium (Nb). Examples of group 6 metals include chromium (Cr) and molybdenum (Mo). Examples of group 7 metals include manganese (Mn). Examples of group 8 metals include iron (Fe) and ruthenium (Ru). Examples of group 9 metals include cobalt (Co). Examples of group 10 metals include nickel (Ni), palladium (Pd), and platinum (Pt). Examples of group 11 metals include copper (Cu), silver (Ag), and gold (Au).

[0031] The preferred elements are metallic and noble metals selected from the fourth to sixth periods and groups 3 to 11 of the periodic table. Cerium, titanium, vanadium, niobium, chromium, molybdenum, manganese, iron, nickel, copper, platinum, and gold are readily available and readily provide the effects of this invention, and are therefore preferred. Iron or titanium is preferred due to their potential toxicity to humans.

[0032] The spherical silica particles contain 0.01 to 40% by mass of a transition metal element. If the content of the transition metal element is 0.01% by mass or more, the spherical silica particles can be given a visually recognizable hue and the dielectric loss tangent can be reduced. If the content of the transition metal element is 40% by mass or less, the high band gap of silica can be maintained, and the dielectric loss tangent can be maintained at a low level. The content of the transition metal element can be adjusted appropriately depending on the amount of transition metal element contained. In the spherical silica particles, it is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, particularly preferably 0.4% by mass or more, and most preferably 1% by mass or more. Furthermore, the upper limit is preferably 30% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, particularly preferably 8% by mass or less, and most preferably 5% by mass or less.

[0033] The content of transition metal elements in spherical silica particles can be determined by inductively coupled plasma (ICP) emission spectroscopy after removing silicon, which is the main component, by adding perchloric acid and hydrofluoric acid to the spherical silica particles and calcining them.

[0034] In addition, in the spherical silica particle powder of this embodiment, elements from Groups 1 to 2 and Groups 12 to 15 of the periodic table can be added to the silica particles loaded with elements as needed, without impairing the effect of the present invention.

[0035] As described above, the spherical silica particle powder of this embodiment contains transition metal elements in the powder by comprising a plurality of spherical silica particles on which transition metal elements are loaded. For the spherical silica particles on which transition metal elements are loaded, the content of the transition metal elements in the powder is not particularly limited as long as it is 0.01 to 40% by mass. Preferably, the spherical silica particle powder contains at least 10% by mass of element-loaded silica particles, more preferably at least 30% by mass, and even more preferably at least 50% by mass. The spherical silica particle powder may also consist of 100% by mass of element-loaded silica particles.

[0036] In addition, as long as the L of spherical silica particle powder * value, a * value and b * The value satisfies √{(a * ) 2 +(b * ) 2 +(100-L * ) 2 If the value is ≥20, it can include particles other than silica particles loaded with elements, such as spherical silica particles without metal elements, alumina, titanium dioxide, titanates, zirconates, and other inorganic particles other than silica.

[0037] Silica particles can be crystalline or amorphous, but amorphous silica is preferred due to its lower biotoxicity and fewer environmental restrictions. The amorphous nature of silica can be confirmed by known methods. Examples of known methods include measuring diffraction peaks originating from silica crystals (e.g., α-SiO2) using X-ray diffraction equipment. It should be noted that in this specification, "amorphous" refers to the absence of distinct diffraction peaks originating from crystals.

[0038] The spherical silica powder contains spherical particles, with a sphericity preferably between 0.75 and 1.0. If the sphericity is low, the specific surface area increases, thus the dielectric loss tangent tends to rise; therefore, a sphericity of 0.75 or higher is preferred. A sphericity of 0.90 or higher is more preferred, and 0.93 or higher is even more preferred; the closer to 1.0, the more preferred.

[0039] Sphericity can be expressed as follows: For any 100 particles in the photographic projection of spherical silica powder obtained by scanning electron microscopy (SEM), their maximum diameter (DL) and orthogonal minor diameter (DS) are measured, and the average value of the calculated ratio of minimum diameter (DS) to maximum diameter (DL) (DS / DL) is used to represent it.

[0040] In this embodiment, the dielectric loss tangent of the spherical silica particles is preferably 0.0030° or less at a frequency of 1 GHz. If the dielectric loss tangent is 0.0030° or less, it becomes a powder with a low dielectric loss tangent, thus enabling the formation of substrates or sheets with improved high-frequency characteristics. It should be noted that, particularly in the determination of the dielectric loss tangent and dielectric constant of the powder, the sample space becomes smaller and the measurement accuracy deteriorates at frequencies above 10 GHz; therefore, measurements taken at a frequency of 1 GHz are used in this invention.

[0041] The dielectric loss tangent of the spherical silica particles is preferably 0.0030° or less, more preferably 0.0025° or less, even more preferably 0.0020° or less, and particularly preferably 0.0015° or less. When used as an electronic material, the smaller the dielectric loss tangent, the better the transmission loss of the circuit can be suppressed; therefore, the lower limit value is not particularly limited.

[0042] Furthermore, the relative permittivity of the spherical silica particles in this embodiment is 3.0 to 5.0 at a frequency of 1 GHz. It is practically difficult to make the relative permittivity less than 3.0; if it is 5.0 or less, dielectric loss can be suppressed to a lower level. A relative permittivity of 3.5 or more is more preferred, further preferred is 4.5 or less, even more preferred is 4.3 or less, and particularly preferred is 4.1 or less.

[0043] The dielectric loss tangent and relative permittivity were measured using a dedicated apparatus (e.g., the "Vector Network Analyzer E5063A" manufactured by KEYCOM Co., Ltd.) via a perturbation-mode resonator method on particulate powder that had been dried according to the method described in the examples. Specifically, in a resin tube with a diameter of 15 mm and a length of 40 mm, the bottom surface was sealed with tape, dried powder was filled, and the tube was tapped 5 times before further filling with powder. This operation was repeated 3 times, and the top surface was sealed with tape to obtain a tube uniformly filled with powder. After measuring the blank in an empty resin tube with a diameter of 15 mm and a length of 40 mm sealed with the same mass of tape, the measurement was performed on the tube uniformly filled with powder, thereby obtaining the dielectric loss tangent and relative permittivity.

[0044] The median particle size (d50) of the spherical silica particles in this embodiment is preferably 0.5 to 20 μm. Typically, coloring materials are 0.5 μm or smaller, which may be limited by nanomaterials, potentially leading to residues in fingerprints when used in cosmetics. If the median particle size is 0.5 μm or larger, it is not limited by nanomaterials, maintains the feel of cosmetics, and significantly reduces the dielectric loss tangent. Furthermore, if the median particle size becomes too large, the particle size value increases, resulting in a thicker minimum sheet thickness when the resin composition containing the spherical silica particles is formed, for example, into a sheet. Therefore, a median particle size of 20 μm or less is preferred. The median particle size of the spherical silica particles is more preferably 0.5 to 10 μm, further preferably 1 to 10 μm, and particularly preferably 1 to 5 μm.

[0045] From the viewpoint of improving the uniform dispersion in various compositions and enhancing the interaction between the spherical silica particles and other components (e.g., resin) in the volume-based particle size distribution curve, the 10% particle size (d10) that represents 10% of the cumulative volume is preferably 0.5 to 5.0 μm, more preferably 1.0 to 5.0 μm, and even more preferably 1.0 to 3.0 μm.

[0046] From the viewpoint of improving the uniform dispersion in various compositions and enhancing the interaction between spherical silica particles and other components (e.g., resins), the ratio of median particle size d50 to 10% particle size d10 (d50 / d10) is preferably greater than 1.0 and less than 5.0, more preferably 1.3 to 4.0, and even more preferably 1.5 to 3.0.

[0047] The maximum particle size (Dmax) of the spherical silica powder is preferably 150 times or less, more preferably 100 times or less, further preferably 50 times or less, and particularly preferably 10 times or less than the median particle size. If the maximum particle size is 150 times or less than the median particle size, it is less likely to become a defect when processing sheets using, for example, spherical silica powder. Furthermore, the maximum particle size is preferably 1.2 times or more than the median particle size, more preferably 1.5 times or more, and further preferably 2 times or more.

[0048] The median particle size is the cumulative 50% particle size based on a volume reference, determined using a laser diffraction-based particle size distribution measuring device (e.g., MicrotracBEL Co., Ltd.'s "MT3300EXII"). Specifically, by measuring particle size distribution using laser diffraction / scattering, and setting the total volume of spherical silica particles to 100%, a cumulative curve is obtained; the median particle size is the particle size at the point where the cumulative volume reaches 50% on this curve.

[0049] The 10% particle size and the maximum particle size were also obtained by the same determination as the median particle size.

[0050] In this embodiment, the particle size distribution of the spherical silica particles is preferably unimodal. The unimodal particle size distribution of the silica particles can be confirmed by the presence of only one peak in the particle size distribution based on laser diffraction scattering.

[0051] In this embodiment, the specific surface area of ​​the spherical silica particles is preferably 0.1 to 5.0 m². 2 The range is / g. If the specific surface area is 0.1m² 2 When the composition contains spherical silica particles of g or higher, the contact points with other components are sufficient, resulting in better integration within the composition. Additionally, the specific surface area is 5.0 m² / g. 2 When the specific surface area is below 0.1 g, the dielectric loss tangent can be reduced, thus exhibiting excellent low dielectric loss tangent even in resin compositions. Furthermore, the small specific surface area improves flowability and dispersibility in resin compositions. A specific surface area of ​​0.1 m² is preferred. 2 / g or more, preferably 0.2m 2 / g or more, further preferably 0.5m 2 / g or more, and preferably 5.0m 2 / g or less, preferably 4.0m 2 / g or less, more preferably 3.5m 2 / g or less, especially preferably 3.0m 2 Below / g. It should be noted that the specific surface area is less than 0.1m². 2 Powder with a density of / g is practically difficult to obtain.

[0052] Specific surface area is determined using a multi-point BET method based on nitrogen adsorption using a specific surface area / pore distribution measuring device (such as MicrotracBEL's "BELSORP-miniII" or Micromeritics' "TRISTAR II"). Specifically, 0.1 g of sample is packed into a glass cell for measurement, vacuum dried at 230°C for 5 hours, and then measured at points where the relative pressure range of 0.05 to 0.25 is logarithmically divided into 11 equal parts. The data obtained are analyzed using the multi-point BET method to obtain the specific surface area.

[0053] Furthermore, the specific surface area A(m²) of the spherical silica particles is... 2 The product of the median particle size (g) and the median particle size d50 (μm), A×d50, is preferably 2.7~5.0 μm·m. 2 / g, more preferably 2.7~4.5μm·m 2 / g, further preferably 2.7~4.0μm·m 2 / g. The theoretical value of A×d50 is 2.7 [from specific surface area = 6 / (silicon dioxide true density 2.2 (g / cm³)]. 3 [A×d50 (μm)] is derived from the median particle size d50. Values ​​smaller than this are difficult to achieve in reality. The larger the value of A×d50, the larger the specific surface area per unit particle size and the larger the dielectric loss tangent. Therefore, A×d50 is preferably 5.0 μm·m. 2 / g or less.

[0054] The spherical silica particles in this embodiment can be treated with a silane coupling agent.

[0055] By treating the surface of spherical silica particles with a silane coupling agent, the amount of residual silanol groups on the surface is reduced, the surface is hydrophobic, which can inhibit water adsorption and improve dielectric loss. Furthermore, when the resin composition is made, the affinity with the resin is improved, and the dispersibility and strength of the resin film are enhanced.

[0056] Types of silane coupling agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, and organosilazane compounds. One type of silane coupling agent can be used, or two or more can be used in combination.

[0057] The amount of silane coupling agent attached is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 5 parts by weight, and even more preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of spherical silica powder. Here, the amount of silane coupling agent attached is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more, and even more preferably 0.1 parts by weight or more, and is also preferably 5 parts by weight or less, and more preferably 2 parts by weight or less, relative to 100 parts by weight of spherical silica powder.

[0058] The surface of the silica particles has been treated with a silane coupling agent, which can be confirmed by detecting the peaks generated by the substituents of the silane coupling agent using IR spectroscopy. Furthermore, the amount of silane coupling agent attached can be determined by the carbon content.

[0059] (Method for manufacturing spherical silica particles)

[0060] The spherical silica particle powder of this embodiment is manufactured by using a spherical silica precursor obtained by a wet process, and loading the silica precursor with at least one of the transition metal elements of the periodic table.

[0061] The wet process refers to a method that includes the following steps: using a liquid as a silica source to gel it, thereby obtaining spherical silica particle powder. By using the wet process, spherical silica particles can be formed, thus eliminating the need for particle shape adjustments through crushing or other methods, resulting in particles with a small specific surface area. However, the wet process has difficulty producing particles significantly smaller than their average particle size, and there is a tendency for the specific surface area to decrease after calcination.

[0062] Examples of wet processes include spraying and emulsion gelation. As an emulsion gelation method, a preferred method is to emulsify a dispersed phase containing a silica precursor and a continuous phase, and then gel the resulting emulsion to obtain spherical silica precursors. As an emulsification method, a preferred method is to supply the dispersed phase containing the silica precursor to the continuous phase via micropores or a porous membrane to produce an emulsion. This produces an emulsion with uniform droplet diameter, resulting in spherical silica particles with uniform particle size. Micromixing and membrane emulsification methods can be used as such emulsification methods. For example, micromixing is disclosed in International Publication No. 2013 / 062105.

[0063] When the obtained silica precursor has a high water content, and the weight reduction rate exceeds 10% after drying at 230°C for 12 hours, it is preferable to dry it to below 10%.

[0064] Examples of drying methods include spray dryers, static drying using dryers, and ventilation treatment of dry air.

[0065] When silica precursors are sintered into large blocks, they can be broken up. However, if the sintering is too strong, even if broken up, they will not become spherical particles, and pulverization will not produce spherical particles.

[0066] Commercially available silica precursors can be used. Examples of spherical silica precursors obtained by wet processing include the Sunsphere (registered trademark) series manufactured by AGC Si-Tech, such as "Sunsphere H-31", "Sunsphere H-33", "Sunsphere H-51", "Sunsphere H-121", "Sunsphere L-51", and "Sunsphere L-52", as well as "HNP-20B" and "SLT-20" manufactured by AGC Si-Tech.

[0067] The average pore size of the silica precursor is preferably 1.0 to 50.0 nm. When the average pore size is 1.0 nm or more, the transition metal element can be sufficiently loaded, and the effects of the present invention can be obtained. In addition, if the average pore size of the silica precursor is 50.0 nm or less, the silica particles can be densified (lower specific surface area) by calcination without leaving pores, thus reducing the dielectric loss tangent. The average pore size is more preferably 2.0 nm or more, further preferably 3.0 nm or more, particularly preferably 5.0 nm or more, and even more preferably 30.0 nm or less, further preferably 20.0 nm or less, and particularly preferably 15.0 nm or less.

[0068] The average pore size was determined using the BJH method based on nitrogen adsorption using a specific surface area / pore distribution measuring device (e.g., MicrotracBEL "BELSORP-miniII", Micromeritics "TRISTAR II", etc.). Specifically, 0.1 g of sample was packed into a glass cell for measurement, vacuum dried at 230 °C for 5 hours, and measurements were taken at points where the relative pressure range of 0.05 to 1.0 was logarithmically divided into 49 equal parts. The data obtained were analyzed using the BJH method to obtain the average pore size.

[0069] The specific surface area of ​​the silica precursor is preferably 100~1000 m². 2 / g. The specific surface area of ​​the silica precursor is 100m². 2 When the content is above / g, it can fully load transition metal elements, achieving the effect of the present invention, which is 1000m. 2 At a concentration of / g or less, the strength of the silica precursor particles is sufficiently high. More preferably, the specific surface area of ​​the silica precursor is 200 m². 2 / g or more, further preferably 400m 2 / g or more, especially preferably 500m 2 / g or more, and more preferably 800m 2 / g or less, more preferably 700m 2 / g or less, especially preferably 650m 2 / g or less.

[0070] The specific surface area is calculated using the method described above.

[0071] The sphericity of the silica precursor is preferably 0.75 or higher. If the sphericity is 0.75 or higher, it is essentially spherical, thus reducing the specific surface area of ​​the particles and preventing protrusion damage due to particle vibration, preventing the active surface from being exposed, thereby enabling low dielectric conversion of the silica particles. A sphericity of 0.90 or higher is more preferred, particularly 0.93 or higher, and since closer to a perfect sphere is preferable, 1.0 is most preferred.

[0072] The sphericity of the silica precursor was determined using the method described above.

[0073] The median particle size (d50) of the silica precursor is preferably 0.5 to 20 μm. If the median particle size is 0.5 μm or more, spherical particles can be formed after calcination to reduce the specific surface area. If it is 20 μm or less, it can be easily used as a filler in easily moldable resins. The median particle size is more preferably 1 μm or more, further preferably 1.5 μm or more, particularly preferably 2 μm or more, and even more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 4 μm or less.

[0074] The median particle size of the silica precursor was determined by the method described above.

[0075] The pore volume (PV) of the silica precursor is preferably 0.1 to 2.0 g / cc. When the pore volume of the silica precursor is 0.1 g / cc or higher, it can effectively load transition metal elements; when it is 2.0 g / cc or lower, it can adequately ensure the amount fed into the container, thus improving productivity. The pore volume of the silica precursor is preferably 0.1 g / cc or higher, more preferably 0.2 g / cc or higher, even more preferably 0.5 g / cc or higher, particularly preferably 0.7 g / cc or higher, and preferably 2.0 g / cc or lower, more preferably 1.7 g / cc or lower, even more preferably 1.5 g / cc or lower, and particularly preferably 1.3 g / cc or lower.

[0076] The pore volume was determined using the BJH method based on nitrogen adsorption using a specific surface area / pore distribution measuring device (e.g., MicrotracBEL "BELSORP-miniII", Micromeritics "TRISTAR II", etc.). Specifically, 0.1 g of sample was packed into a glass cell for measurement, vacuum dried at 230 °C for 5 hours, and measurements were taken at points where the relative pressure range of 0.05 to 1.0 was logarithmically divided into 49 equal parts. The data obtained were analyzed using the BJH method to obtain the pore volume.

[0077] Furthermore, the weight reduction rate of the silica precursor after drying at 230°C for 12 hours is preferably 10% or less. If the weight reduction rate is 10% or less, when the silica precursor is calcined with its particles in contact with each other, the particles are less likely to sinter together, and spherical silica powder particles are easily obtained.

[0078] The weight reduction rate is more preferably 9% or less, further preferably 8% or less, and particularly preferably 6% or less. In addition, it is desirable that there is no weight change even when drying at 230°C for 12 hours, so the lower limit is not particularly limited.

[0079] Furthermore, the weight loss on ignition of the silica precursor is preferably 5.0 to 15.0% by mass. Weight loss on ignition is the sum of the mass of water adhering to the silica precursor and the mass of water generated by the condensation of silanol groups contained in the silica precursor. Since the silica precursor has a moderate amount of silanol groups, condensation occurs during calcination, and the number of silanol groups is easily reduced. If the weight loss on ignition is too high, the yield during calcination decreases, and productivity deteriorates. Therefore, the weight loss on ignition of the silica precursor is more preferably 13.0% by mass or less, and most preferably 12.0% by mass or less. If the weight loss on ignition is too low, silanol groups are easily retained during calcination. Therefore, the weight loss on ignition of the silica precursor is more preferably 6.0% by mass or more, and most preferably 7.0% by mass or more.

[0080] Here, the loss on ignition is calculated according to JIS K0067:1992 as the mass loss when 1g of silica precursor is heated and dried at 850°C for 0.5 hours.

[0081] In the manufacturing method of this embodiment, a transition metal element is loaded onto the silica precursor, but it is preferable to first clean the silica precursor. Cleaning is preferably performed using, for example, hydrochloric acid, sulfuric acid, or nitric acid.

[0082] Specifically, when hydrochloric acid is used for cleaning, the silica precursor is dispersed in an aqueous hydrochloric acid solution, followed by solid-liquid separation. The filter cake is then washed with water and dried. This process yields the silica precursor in a granular powder state.

[0083] Next, a transition metal element is added to the silica precursor. Specific and preferred examples of the transition metal element are as described above. The transition metal element exists in the form of oxides, hydrates, chlorides, nitrates, sulfates, etc. For example, if it is iron (Fe), ferric sulfate hydrate can be used; if it is chromium (Cr), chromium nitrate hydrate can be used; if it is nickel (Ni), nickel nitrate hydrate can be used; if it is cerium (Ce), cerium nitrate hydrate can be used; if it is cobalt (Co), cobalt sulfate hydrate can be used; if it is titanium (Ti), titanium sulfate can be used; if it is niobium (Nb), niobium chloride can be used; if it is vanadium (V), vanadium chloride can be used; if it is gold (Au), tetrachloroaurate hydrate can be used; and if it is platinum (Pt), platinum chloride can be used.

[0084] A cleaned silica precursor is added to a solution in which a compound containing a transition metal element is dissolved in a solvent, and the solution is reacted. Examples of solvents include water, alcohols, and acetone.

[0085] Regarding the mixing ratio of the silica precursor and the compound containing the transition metal element, it is preferable to mix them such that the final spherical silica powder contains 0.01 to 40% by mass of the transition metal element. The amount of the compound containing the transition metal element is preferably in the range of 0.01 to 50 parts by mass relative to 100 parts by mass of the silica precursor. The content of the compound containing the transition metal element is more preferably 0.1 parts by mass or more, further preferably 0.2 parts by mass or more, even more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less.

[0086] As a mixing method, mixing devices such as evaporators, Henschel mixers, and Notta mixers can be used.

[0087] After thoroughly mixing a silica precursor with a compound containing a transition metal element, the mixture is dried to form a granular powder, which is then calcined. Through calcination, the transition metal element is fixed within the voids of the silica precursor, and the silica precursor is solidified and densified, while the number of silanol groups on the surface is reduced. As a result, the silica granular powder exhibits a certain hue and can reduce the dielectric loss tangent.

[0088] The heat treatment temperature during calcination is preferably 700~1600℃. If the treatment temperature is too low, calcination takes longer and productivity decreases. Conversely, if the temperature is too high, particles tend to aggregate, and the particle size in the resin composition tends to increase. The treatment temperature is more preferably 800℃ or higher, more preferably 900℃ or higher, and even more preferably 1500℃ or lower, and even more preferably 1400℃ or lower.

[0089] The heat treatment time can be adjusted appropriately according to the equipment used, the roasting temperature, etc. For example, it is preferred to perform the heat treatment for 0.5 to 50 hours, and more preferably 1 to 10 hours.

[0090] The atmosphere during heat treatment can be either oxygen-containing or oxygen-free. For example, it can be calcined in an atmospheric atmosphere, a hydrogen atmosphere, or a nitrogen atmosphere, depending on the transition metal element being loaded.

[0091] There are no particular limitations on the heat treatment method. Examples include heat treatment based on static placement, heat treatment based on rotary kiln, and heat treatment based on spray combustion.

[0092] Spherical silica particles sometimes exhibit weak sintering after calcination, thus requiring crushing. To avoid compromising the effectiveness of the invention and to maintain sphericity and surface area, crushing is preferably performed with a particle sphericity of not less than 0.75. Furthermore, it is preferable that the surface area does not increase due to the crushing process. A significant increase in surface area during crushing refers to the pulverization of some spherical particles, resulting in fine surface damage and the formation of micropowder. An increase in surface area leads to increased viscosity when dispersed in resin and a deterioration of the dielectric loss tangent, which is therefore undesirable.

[0093] Crushing can be carried out using crushing devices such as cyclone mills, jet mills, impact mills, and Wand crushers. In addition, crushing can also be carried out using agate mortars and vibrating screens.

[0094] The calcined spherical silica particles can also be surface-treated with a silane coupling agent. Through this process, the silanol groups on the surface of the spherical silica particles react with the silane coupling agent, reducing the number of silanol groups on the surface and improving the dielectric loss tangent. Furthermore, the surface becomes hydrophobic, improving its affinity for resins and thus enhancing resin dispersibility.

[0095] There are no particular restrictions on the surface treatment conditions; they can be any standard surface treatment conditions, and either wet or dry treatment methods can be used. From the viewpoint of achieving uniform treatment, wet treatment is preferred.

[0096] Examples of silane coupling agents used in surface treatment include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, and organosilazane compounds. One or more of these can be used in combination.

[0097] Specifically, as surface treatment agents, examples include: aminopropylmethoxysilane, aminopropyltriethoxysilane, ureopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-2-(aminoethyl)aminopropyltrimethoxysilane, and other aminosilane-based coupling agents; epoxypropoxypropyltrimethoxysilane, epoxypropoxypropyltriethoxysilane, epoxypropoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, and other epoxysilane-based coupling agents; mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, and other mercaptosilane-based coupling agents; methyltrimethoxysilane, vinyltrimethoxysilane, octadecane, etc. Silane coupling agents such as trimethoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole silane, and triazine silane; CF3(CF2)7CH2CH2Si(OCH3)3, CF3(CF2)7CH2CH2SiCl3, CF3(CF2)7CH2CH2Si(CH3)(OCH3)2, CF3(CF2)7CH2CH2Si(CH3)Cl2, CF3(CF2)5CH2CH2SiCl3, CF3(CF2)5CH2CH2Si(OCH3)3, CF3CH2CH2SiCl3, CF3CH2CH2Si(OCH3)3, C8F 17 SO2N(C3H7)CH2CH2CH2Si(OCH3)3, C7F 15 CONHCH2CH2CH2Si(OCH3)3、C8F 17 CO2CH2CH2CH2Si(OCH3)3、C8F 17 Fluorosilane coupling agents such as -O-CF(CF3)CF2-O-C3H6SiCl3 and C3F7-O-(CF(CF3)CF2-O)2-CF(CF3)CONH-(CH2)3Si(OCH3)3; organosilane compounds such as hexamethyldisilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, and 1,1,3,3,5,5-hexamethylcyclotrisilazane.

[0098] The amount of silane coupling agent used is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and even more preferably 0.10 parts by mass or more, relative to 100 parts by mass of spherical silica particles. It is also preferably 5 parts by mass or less, and more preferably 2 parts by mass or less.

[0099] Examples of methods for treating silica particles with silane coupling agents include: a dry method of spraying silane coupling agents into spherical silica particles; and a wet method of dispersing spherical silica particles in a solvent and then adding silane coupling agents to allow them to react.

[0100] (Resin composition and slurry composition)

[0101] The spherical silica particles of this embodiment exhibit good dispersibility in various solvents and excellent mixability in resin compositions.

[0102] The resin composition of this embodiment comprises the spherical silica particle powder of this embodiment and resin. The content of the spherical silica particle powder is preferably 5 to 90% by mass relative to the total resin composition. When the content of the spherical silica particle powder is 5% by mass or more, sufficient peel strength and sufficient coloring effect can be obtained, and when it is 90% by mass or less, the viscosity of the resin composition will not increase excessively, making it easy to handle. From the viewpoint of improving peel strength and coloring effect, the content of the spherical silica particle powder in the resin composition is more preferably 10% by mass or more, further preferably 15% by mass or more, and from the viewpoint of making it easier to handle, more preferably 85% by mass or less, further preferably 80% by mass or less, particularly preferably 75% by mass or less, and most preferably 70% by mass or less.

[0103] As resins, one or more of the following can be used: epoxy resin, silicone resin, phenolic resin, melamine resin, urea-formaldehyde resin, unsaturated polyester resin, fluororesin, polyimide resin, polyamide-imide resin, polyetherimide, etc.; polyester resins such as polybutylene terephthalate and polyethylene terephthalate; polyphenylene ether resin, polyphenylene sulfide resin, phenolic resin, o-divinylbenzene resin, aromatic polyester resin, polysulfone, liquid crystal polymer, polyethersulfone, polycarbonate, maleimide modified resin, ABS (acrylonitrile-butadiene-styrene) resin, AAS (acrylonitrile-acrylic rubber-styrene) resin, AES (acrylonitrile-ethylene-propylene-diene rubber-styrene) resin, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-ethylene copolymer (ETFE). The dielectric loss tangent in the resin composition also depends on the properties of the resin, so these factors should be taken into account when selecting the resin to use.

[0104] Thermosetting resins are preferred. A single thermosetting resin can be used, or two or more can be used in combination. Examples of thermosetting resins include epoxy resins, polyphenylene ether resins, polyimide resins, phenolic resins, and o-divinylbenzene resins. From the viewpoints of adhesion and heat resistance, epoxy resins, polyphenylene ether resins, or o-divinylbenzene resins are preferred thermosetting resins.

[0105] From the perspective of adhesion and dielectric properties, the weight-average molecular weight of thermosetting resins is preferably 1000-7000, more preferably 1000-5000, and even more preferably 1000-3000. The weight-average molecular weight is determined by gel permeation chromatography (GPC) using polystyrene conversion.

[0106] From the viewpoints of suppressing uneven distribution of silica particles, reducing water absorption, low dielectric loss tangent, and improving adhesion, the content of spherical silica particle powder relative to 100 parts by weight of thermosetting resin is preferably 10 to 400 parts by weight, more preferably 50 to 300 parts by weight, and even more preferably 70 to 250 parts by weight. In particular, when it is desired that the silica particles are highly packed, the content of the spherical silica particle powder is preferably 80 parts by weight or more, more preferably 90 parts by weight or more.

[0107] Through the aforementioned mechanism, the spherical silica particles are in a fully wetted and uniformly dispersed state, and also readily interact with the thermosetting resin. Therefore, in this composition with a content within this range, i.e., in which the spherical silica particles are more abundant than the thermosetting resin, both components are easily stabilized, enabling the formation of a molded product with excellent adhesion to the metal substrate layer.

[0108] Furthermore, the spherical silica particles of this embodiment can be used as a filler material in a slurry composition. A slurry composition refers to a mud-like composition in which the spherical silica particles of this embodiment are dispersed in an aqueous or oil-based medium.

[0109] The content of spherical silica particles relative to the overall slurry composition is preferably 1 to 80% by mass, more preferably 20 to 80% by mass, even more preferably 40 to 80% by mass, and particularly preferably 50 to 80% by mass. By containing spherical silica particles in this proportion, the viscosity of the dispersion can be appropriately maintained.

[0110] Examples of oil-based media include acetone, methanol, ethanol, butanol, 2-propanol, 1-propanol, isobutanol, 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, propyl acetate, isobutyl acetate, butyl acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methylpyrrolidone, n-hexane, n-heptane, cyclohexane, methylcyclohexane, cyclohexanone, and naphtha as a mixture. These can be used individually or in mixtures of two or more.

[0111] In addition to the resin and medium described above, the resin composition and slurry composition may contain any other components. Examples of such components include, for instance, surfactants and fillers other than silica. Furthermore, dispersing agents may be added to improve dispersibility.

[0112] The dispersion of spherical silica particles in various compositions can be achieved using dispersion devices similar to those used in pigment dispersion. Examples include: dispersers, homogenizers, planetary mixers, homogenizers (e.g., M Technique's "CLEARMIX", PRIMIX's "FILMIX", Silverson's "Abramix"), paint mixers (Red Devil), colloid mills (e.g., PUC's "PUC colloid mill", IKA's "colloid mill MK"), conical mills (e.g., IKA's "cone mill MKO"), ball mills, sand mills (e.g., Shinmaru Enterprises' "Dyno mill"), grinding mills, bead mills (e.g., Eirich's "DCPmill"), media dispersers such as coball mills, wet jet mills (e.g., Genus PY, SuginoMachine's "Star Burst", Nanozer's "Nanomizer"), and M Technique's "CLEAR" mill. Media-free dispersers such as the "SS-5" and "CROS" manufactured by Nara Machinery Co., Ltd., as well as other roller mills and kneaders, are preferred. It is preferable not to use grinding media (balls, beads, etc.). This is because there is a concern about contamination from abrasive media if grinding media are used. Specifically, media-free dispersers such as wet jet mills (Genus PY manufactured by Genus Co., Ltd., Starburst manufactured by Sugino Machine Co., Ltd., and "Nanomizer" manufactured by Nanozer Co., Ltd.), "CLEAR SS-5" manufactured by M-Technique Co., Ltd., and "MICROS" manufactured by Nara Machinery Co., Ltd. are preferred.

[0113] Furthermore, the dispersion process is preferably carried out at a temperature of 0 to 100°C. By performing the dispersion process within this temperature range, the viscosity of the solvent can be appropriately maintained, thus preserving productivity. Additionally, solvent evaporation can be suppressed, making it easier to control the solid content. The processing temperature is preferably 0 to 100°C, more preferably 5 to 90°C, and even more preferably 10 to 80°C. Here, the processing temperature is more preferably 5°C or higher, even more preferably 10°C or higher, and even more preferably 90°C or lower, and even more preferably 80°C or lower.

[0114] The dispersion time should be set appropriately according to the dispersion device used so as not to cause particle damage. It is preferably 0.5 to 60 minutes, more preferably 0.5 to 10 minutes, and even more preferably 0.5 to 5 minutes.

[0115] Then, the aggregates of spherical silica particles that remain even after dispersion treatment are wet-classified. Examples of wet classification include classification using sieves or centrifugal force. When using a sieve, it is preferable to use a sieve with a mesh size of 100 μm or less. For example, a metal sieve with a dense lattice structure, such as an electroforming sieve, is preferably used.

[0116] The mesh size of the sieve is preferably 0.2 to 100 μm, more preferably 0.5 to 75 μm, even more preferably 0.5 to 50 μm, and particularly preferably 1 to 35 μm. Here, the mesh size of the sieve is preferably 100 μm or less, more preferably 75 μm or less, even more preferably 50 μm or less, and particularly preferably 35 μm or less. Furthermore, it is preferably 0.2 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more.

[0117] Then, it can be diluted or concentrated as needed to adjust to an appropriate concentration. Methods of concentration include gasification concentration and solid-liquid separation.

[0118] It should be noted that in the method for manufacturing the slurry composition of this embodiment, a silane coupling agent may be added to the mixture of solvent and spherical silica particle powder. Examples of silane coupling agents include the aforementioned silane coupling agents.

[0119] The spherical silica particles of this embodiment can be used as various filler materials, and are particularly suitable as filler materials for resin compositions used in the manufacture of electronic substrates for personal computers, laptops, digital cameras, and communication devices such as smartphones and game consoles. Specifically, in order to reduce dielectric loss tangent, reduce transmission loss, reduce moisture absorption, and improve peel strength, the silica particles of this embodiment are also expected to be used in resin compositions, prepregs, metal-clad laminates, printed circuit boards, resin sheets, adhesive layers, adhesive films, solder resists, bump reflow soldering, redistribution insulating layers, chip bonding materials, sealing materials, underfills, mold underfills, and multilayer inductors.

[0120] (Cosmetic composition)

[0121] Furthermore, the spherical silica particles of this embodiment are not limited to nanomaterials, and therefore can be suitable for use as cosmetic materials. By including the spherical silica particles of this embodiment in a cosmetic composition, cosmetics with a desired hue can be obtained.

[0122] As cosmetics, examples include foundation, loose powder, lotion, base lotion, lipstick, and sunscreen. The amount of spherical silica particles they contain can be appropriately set according to their intended purpose.

[0123] As described above, the present invention includes the following: <1> ~ <12> The composition of.

[0124] <1> A spherical silica particle powder, comprising multiple spherical silica particles loaded with elements.

[0125] The spherical element-loaded silica particles are particles in which at least one of the transition metal elements of the periodic table is loaded onto spherical silica particles.

[0126] The spherical silica particles contain 0.01 to 40% by mass of the transition metal element.

[0127] The spherical silica particle powder is conformed to CIE-standardized L... * a * b * L in the colorimetric system * value, a * value and b * The value satisfies √{(a * ) 2 +(b * ) 2 +(100-L * ) 2 ≥20.

[0128] <2> According to the above <1> The spherical silica particles powder has a median particle size of 0.5~20μm.

[0129] <3> According to the above <1> or <2> The spherical silica particle powder has a specific surface area of ​​0.1~5.0 m². 2 / g.

[0130] <4> According to the above <1> ~ <3> The spherical silica particle powder described in any one of the above statements, wherein the specific surface area A (m²) of the spherical silica particle powder is... 2 The product of the median particle size (g) and the median particle size d50 (μm), A×d50, is 2.7~5.0 μm·m. 2 / g.

[0131] <5> According to the above <1> ~ <4> The spherical silica particle powder as described in any one of the following descriptions, wherein the transition metal element is a metal element of the fourth to sixth period and group 3 to group 11 of the periodic table.

[0132] <6> According to the above <1> ~ <5> The spherical silica particle powder described in any one of the following methods has a relative permittivity of 3.0 to 5.0 at a frequency of 1 GHz.

[0133] <7> A method for manufacturing spherical silica particle powder, wherein the method comprises the following: <1> ~ <6> The method for manufacturing spherical silica particles according to any one of the following methods comprises: using a spherical silica precursor obtained by a wet process, loading the silica precursor with at least one of the transition metal elements of the periodic table.

[0134] <8> According to the above <7> The method for manufacturing spherical silica particles, wherein the pore volume of the silica precursor is 0.1~2.0 g / cc.

[0135] <9> According to the above <7> or <8> The method for manufacturing spherical silica particles, wherein the specific surface area of ​​the silica precursor is 100~1000 m². 2 / g.

[0136] <10> A resin composition comprising 5-90% by weight of the aforementioned <1> ~ <6> The spherical silica particle powder described in any one of the following statements.

[0137] <11> A slurry composition comprising 1-80% by mass of the aforementioned... <1> ~ <6> The spherical silica particle powder described in any one of the following statements.

[0138] <12> A cosmetic composition comprising the above. <1> ~ <6> The spherical silica particle powder described in any one of the following statements.

[0139] Example

[0140] The present invention will now be described in detail with reference to the embodiments, but the present invention is not limited to these embodiments. In the following description, common ingredients are used interchangeably. In addition, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass". Examples 1 to 38 are examples, and Example 39 is a comparative example.

[0141] The added compounds used in the following examples are described below.

[0142] Ferric(II) sulfate heptahydrate, chromium(III) nitrate nonahydrate, nickel(III) nitrate hexahydrate, and titanium(IV) sulfate solution: prepared by Kanto Chemical Company.

[0143] Cerium(III) nitrate hexahydrate: manufactured by Pure Chemical Company

[0144] Cobalt(II) sulfate heptahydrate, niobium(V) chloride, vanadyl(V) trichlorochlorochloride, tetrachloroauro(III) acid tetrahydrate, platinum(II) chloride, tetrachloroauro(III) acid tetrahydrate, copper(II) sulfate pentahydrate, gold(III) chloride, silver nitrate, ferric(III) chloride hexahydrate, magnesium sulfate (anhydrous), boric acid: manufactured by Fujifilm and Koko Pure Chemical Industries Co., Ltd.

[0145] Calcium acetate tetrahydrate: manufactured by Aldrich

[0146] (Example 1)

[0147] As a precursor for spherical silica, silica particles (Sunsphere H-31, manufactured by AGC Si-Tech, with a median particle size (d50) of 3 μm, a pore volume (PV) of 1.00 g / cc, and a BET specific surface area of ​​650 m²) manufactured by wet process were used. 2 / g, oil absorption 150mL / 100g).

[0148] 100g of spherical silica precursor was dispersed in 1L of 1M hydrochloric acid, and then solid-liquid separation was performed. The resulting filter cake was washed with 10L of distilled water and dried under vacuum at 200℃ to obtain cleaned silica granular powder.

[0149] Place 100g of cleaned silica particles into a container, add a solution made by dissolving 6g of ferric sulfate(II) heptahydrate (manufactured by Kanto Chemical Co., Ltd.) in 80ml of water, and mix for 3 minutes at 2000rpm using a rotary mixer (ARE-310, manufactured by Shinki Co., Ltd.).

[0150] Then, it was dried in an oven at 200°C for 4 hours, followed by atmospheric calcination at 1150°C for 1 hour. The resulting powder was pulverized using a Wand crusher to obtain 100g of element-loaded silica particle powder 1.

[0151] (Example 2~Example 19)

[0152] As shown in Table 1, the added compounds and their amounts, as well as the loading conditions, were changed, and otherwise, silica particles 2-19 loaded with elements were obtained in the same manner as in Example 1.

[0153] (Example 20)

[0154] As a precursor for spherical silica, silica particles (Sunsphere H-51, manufactured by AGC Si-Tech, with a median particle size (d50) of 5 μm, a pore volume (PV) of 0.8 g / cc, and a BET specific surface area of ​​700 m²) manufactured by wet process were used. 2 / g, oil absorption 150mL / 100g), and the calcination atmosphere was set to nitrogen. Otherwise, the same as in Example 1, silica particle powder 20 loaded with elements was obtained.

[0155] (Example 21)

[0156] As a spherical silica precursor, silica particles (Sunsphere H-121, manufactured by AGC Si-Tech, with a median particle size (d50) of 12 μm, a pore volume (PV) of 0.8 g / cc, and a BET specific surface area of ​​680 m²) manufactured by a wet process were used. 2 / g, oil absorption 150mL / 100g), and the calcination atmosphere was set to nitrogen. Otherwise, the same as in Example 1, silica particle powder 21 loaded with elements was obtained.

[0157] (Example 22)

[0158] As a spherical silica precursor, silica particles (Sunsphere H-33, manufactured by AGC Si-Tech, with a median particle size (d50) of 4 μm, a pore volume (PV) of 1.7 g / cc, and a BET specific surface area of ​​700 m²) manufactured by wet process were used. 2 / g, oil absorption 400mL / 100g), and the calcination atmosphere was set to nitrogen. Otherwise, the same as in Example 1, silica particle powder 22 loaded with elements was obtained.

[0159] (Example 23)

[0160] As a spherical silica precursor, silica particles (Sunsphere L-51, manufactured by AGC Si-Tech, with a median particle size (d50) of 5 μm, a pore volume (PV) of 0.7 g / cc, and a BET specific surface area of ​​420 m²) manufactured by wet process were used. 2 / g, oil absorption 150mL / 100g), and the calcination atmosphere was set to nitrogen. Otherwise, the same as in Example 1, silica particle powder 23 loaded with elements was obtained.

[0161] (Example 24)

[0162] As a spherical silica precursor, silica particles (Sunsphere L-52, manufactured by AGC Si-Tech, with a median particle size (d50) of 5 μm, a pore volume (PV) of 1.3 g / cc, and a BET specific surface area of ​​400 m²) manufactured by wet process were used. 2 / g, oil absorption 300mL / 100g), and the calcination atmosphere was set to nitrogen. Otherwise, the same as in Example 1, silica particle powder 24 loaded with elements was obtained.

[0163] (Example 25)

[0164] As a spherical silica precursor, silica particles (Sunsphere H-31, manufactured by AGC Si-Tech, with a median particle size (d50) of 4 μm, a pore volume (PV) of 0.1 g / cc, and a BET specific surface area of ​​200 m²) manufactured by wet process were used. 2 The same method as in Example 1 was used to obtain cleaned silica particle powder (with an oil absorption of 150 mL / 100 g). Next, the cleaned silica particle powder was calcined at 800°C for 1 hour to obtain calcined silica particle powder.

[0165] Place 100g of calcined silica granules into a container, add a solution made by dissolving 6g of ferric sulfate(II) heptahydrate (manufactured by Kanto Chemical Co., Ltd.) in 80ml of water, and mix for 3 minutes at 2000rpm using a rotary mixer (ARE-310, manufactured by Shinki Co., Ltd.).

[0166] Then, after drying in an oven at 200°C for 4 hours, it was calcined under nitrogen at 1240°C for 1 hour. The resulting granular powder was crushed using a Wande crusher to obtain 100g of element-loaded silica granular powder 25.

[0167] (Example 26)

[0168] The amount of ferric(II) sulfate heptahydrate added was set to 3g, and otherwise, silica particle powder 26 loaded with the element was obtained in the same manner as in Example 23.

[0169] (Example 27)

[0170] The amount of ferric(II) sulfate heptahydrate added was set to 3g, and otherwise, silica particle powder 27 loaded with elements was obtained in the same manner as in Example 25.

[0171] (Example 28)

[0172] The amount of ferric(II) sulfate heptahydrate added was set to 3g, and otherwise, silica particle powder 28 loaded with the element was obtained in the same manner as in Example 24.

[0173] (Example 29~Example 36)

[0174] As shown in Table 2, the added compounds and their amounts, as well as the loading conditions, were changed, and otherwise, silica particles 29-36 loaded with elements were obtained in the same manner as in Example 1.

[0175] (Example 37~Example 38)

[0176] As shown in Table 2, the added compounds and their amounts, as well as the loading conditions, were changed and calcined at 800°C. Otherwise, the same as in Example 1, silica particles 37-38 loaded with elements were obtained.

[0177] (Example 39)

[0178] The silica particles before loading with metal elements were used as the comparison objects in Examples 1 to 38.

[0179] As a spherical silica precursor, silica particles (Sunsphere H-31, manufactured by AGC Si-Tech, with a median particle size (d50) of 3 μm, a pore volume (PV) of 1.00 g / cc, and a BET specific surface area of ​​650 m²) manufactured by wet process were used. 2 / g, oil absorption 150mL / 100g).

[0180] 100g of spherical silica precursor was dispersed in 1L of 1M hydrochloric acid, and then solid-liquid separation was performed. The resulting filter cake was washed with 10L of distilled water and dried under vacuum at 200℃ to obtain cleaned silica granular powder.

[0181] The cleaned silica granules were calcined at 1200°C for 1 hour, and the resulting granules were crushed using a Wande crusher to obtain 100g of silica granules 39.

[0182] The spherical silica particles from Examples 1 to 39 were evaluated as follows. The results are shown in Tables 1 and 2.

[0183] "evaluate"

[0184] <Relative permittivity, dielectric loss tangent>

[0185] Using a dedicated instrument (Vector Network Analyzer E5063A, manufactured by KEYCOM), the perturbation resonator method was employed to measure silica particles at a test frequency of 1 GHz, a test temperature of approximately 24 °C, a humidity of approximately 45%, and three measurements.

[0186] First, the powder was vacuum dried at 150°C. One end of a 15mm diameter × 40mm length polytetrafluoroethylene (PTFE) tube was sealed with Teflon (registered trademark) tape. The dried powder was then filled into the tube, and after tapping it 5 times, more powder was added. This process was repeated 3 times. The open end of the tube was then sealed with Teflon tape to obtain a PTFE tube uniformly filled with powder. After measuring the blank using an empty PTFE tube (15mm diameter × 40mm length) sealed with the same mass of Teflon tape, measurements were performed on the PTFE tube uniformly filled with powder. The relative permittivity and dielectric loss tangent were calculated using the powder filling rate in the container.

[0187] <Metal element content>

[0188] Perchloric acid and hydrofluoric acid were added to silica granules and calcined to remove silicon, which is the main component. Then, the content of metal elements was determined by inductively coupled plasma (ICP) emission spectroscopy.

[0189] <Particle size (median particle size)>

[0190] The median particle size was determined using a particle size distribution measuring device (MicrotracBEL MT3300EXII) employing laser diffraction. The spherical silica particles were dispersed by ultrasonic waves irradiating the device three times for 60 seconds before measurement. Each measurement was performed twice for 60 seconds, and the average value was calculated.

[0191] Specific surface area

[0192] The silica powder particles were dried under reduced pressure at 230°C to completely remove moisture, thus preparing a sample. The specific surface area of ​​this sample was determined using a Micromeritics Tristar II automated surface area / pore distribution measuring device via the multi-point BET method under nitrogen atmosphere.

[0193] <L * a * b * Measurement >

[0194] After filling the glass bath with silica powder, it was tapped 30 times to confirm a smooth, compacted powder, and the hue of the glass bath was observed. Additionally, the color value L was measured using a spectrophotometer (SE-7700, manufactured by Nippon Denshoku Kogyo Co., Ltd.). * value, a * value, b * value.

[0195] By L * value, a * value, b * Find the value of the following formula (1).

[0196] Equation (1): √{(a * ) 2 +(b * ) 2 +(100-L * ) 2}

[0197] [Table 1]

[0198]

[0199] [Table 2]

[0200]

[0201] As shown in Tables 1 and 2, the spherical silica particles in Examples 1 to 38 were all colored, with a value of 20 or higher for Formula (1), exhibiting a color tone that was sufficiently visually recognizable. In addition, the dielectric loss tangent of the spherical silica particles in Examples 1 to 38 was also small.

[0202] The present invention has been described in detail with reference to specific embodiments, but it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2024-028872, filed on February 28, 2024, the contents of which are incorporated herein by reference.

Claims

1. A spherical silica particle powder, comprising multiple spherical silica particles loaded with elements. The spherical element-loaded silica particles are particles in which at least one of the transition metal elements of the periodic table is loaded onto spherical silica particles. The spherical silica particles contain 0.01 to 40% by mass of the transition metal element. The spherical silica particle powder is conformed to CIE-standardized L... * a * b * L in the colorimetric system * value, a * value and b * The value satisfies √{(a*)} 2 +(b*) 2 +(100-L*) 2 ≥20.

2. The spherical silica particle powder according to claim 1, wherein, The median particle size of the spherical silica particles is 0.5~20μm.

3. The spherical silica particle powder according to claim 1, wherein, The specific surface area of ​​the spherical silica particles is 0.1~5.0 m². 2 / g.

4. The spherical silica particle powder according to claim 1, wherein, The specific surface area A(m²) of the spherical silica particles is... 2 The product of the median particle size (g) and the median particle size d50 (μm), A×d50, is 2.7~5.0 μm·m. 2 / g.

5. The spherical silica particle powder according to claim 1, wherein, The transition metal elements are those in the fourth to sixth periods and groups 3 to 11 of the periodic table.

6. The spherical silica particle powder according to claim 1, wherein, The relative permittivity of the spherical silica particles is 3.0~5.0 at a frequency of 1 GHz.

7. A method for manufacturing spherical silica particle powder, as described in any one of claims 1 to 6, comprising: Using a spherical silica precursor obtained by a wet process, the silica precursor is loaded with at least one of the transition metal elements of the periodic table.

8. The method for manufacturing spherical silica particle powder according to claim 7, wherein, The pore volume of the silica precursor is 0.1~2.0 g / cc.

9. The method for manufacturing spherical silica particle powder according to claim 7, wherein, The specific surface area of ​​the silica precursor is 100~1000 m². 2 / g.

10. A resin composition comprising 5 to 90% by mass of spherical silica particles according to any one of claims 1 to 6.

11. A slurry composition comprising 1 to 80% by mass of spherical silica particles according to any one of claims 1 to 6.

12. A cosmetic composition comprising spherical silica particles as described in any one of claims 1 to 6.

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