Particulate material and method for producing same
Patent Information
- Application Number
- PCT/JP2025/013016
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2025-03-28
- Publication Date
- 2026-10-01
Smart Images
Figure JPOXMLDOC01-APPB-T000001
Abstract
Description
Particulate material and method for producing the same
[0001] The present invention relates to a particulate material that can be used by being dispersed in an organic solvent, and a method for producing the same.
[0002] Conventionally, resin compositions obtained by dispersing a filler material made of a metal oxide in a resin material have been widely used. Dispersing the filler material made of a metal oxide improves the mechanical properties of the resin composition and its cured product. In such a resin composition, it is desirable that the filler material is uniformly dispersed. In order to obtain such a resin composition, the filler material can be directly dispersed in the resin material, or a slurry composition obtained by dispersing the filler material in an organic solvent can be produced and then mixed into the resin material to obtain the resin composition.
[0003] Japanese Patent Application Laid-Open No. 2014-133697, Japanese Patent Application Laid-Open No. 2005-298740, Japanese Patent Application Laid-Open No. 2010-501707
[0004] The present invention has been completed in view of the above circumstances, and an object to be solved is to provide a particulate material which is a metal oxide particulate material having particularly high dispersibility in an organic solvent and a method for producing the same.
[0005] For the purpose of solving the above problems, the present inventors have conducted intensive studies. As a result, they have found that by reacting a predetermined amount of water with the surface treatment agent in advance, the surface treatment agent can be sufficiently reacted with the surface-treated particulate material, and the dispersibility of the particulate material in toluene is improved, and the present invention described below has been completed. (1) That is, the method for producing a particulate material of the present invention comprises a surface treatment step of performing a surface treatment on a raw particulate material composed of an inorganic material using a surface treatment agent composition containing a surface treatment agent containing a silane compound and water to obtain a treated particulate material, wherein the amount of the surface treatment agent composition and the surface treatment conditions in the surface treatment step are: surface area per 1 g H (m ２The C / H value calculated from the carbon content C (mass%) is set to be 0.015 or more and 0.045 or less, the C / H value after washing the treated particle material is set to be 0.013 or more and 0.032 or less, the theoretical number of moles of functional groups A (mol / 100g) / H calculated from the C of the treated particle material after washing is set to be 0.0003 or more, and the D100 in the particle size distribution measured by dry method is 800 μm or less.
[0006] The surface treatment agent is preferably vinyltrimethoxysilane.
[0007] Furthermore, the raw material particle material is preferably a metal oxide obtained by deflagrating a metal particle material made of metal in a high-temperature oxidizing atmosphere and then rapidly cooling it. This method is known as the VMC method and is a method that can suitably produce perfectly spherical particles.
[0008] Furthermore, the dispersibility of the treated particle material can be improved by limiting the amount of methanol contained in the surface treatment agent composition.
[0009] Specifically, the surface treatment agent has a methoxy group, and it is preferable that the surface treatment agent composition is mixed with 4% by mass or more of water based on the mass of the surface treatment agent, and then brought into contact with the raw material particle material in the surface treatment step before the methanol content exceeds 5% by mass based on the total mass of the surface treatment agent composition.
[0010] Furthermore, it is preferable to have a classification step after the surface treatment step in which coarse particles of a predetermined particle size or larger are classified and removed. (2) The particle material of the present invention that solves the above problems has a surface area H (m²) per gram ２The C / H value calculated from the carbon content C (mass%) is 0.015 or more and 0.045 or less, the C / H value after washing is 0.013 or more and 0.032 or less, the theoretical number of moles of functional groups A (mol / 100g) / H calculated from the C after washing is 0.0003 or more, it contains more than 0 ppm and 400 ppm of moisture based on the total mass, the D100 in the particle size distribution measured by dry method is 800 μm or less, the surface is treated so that when 10 g of powder is dispersed in 40 g of toluene with ultrasound for 30 minutes and left to stand in a 110 mL glass bottle for 30 minutes, the supernatant is less than 20 mm, the volume average particle size is 0.1 μm or more and 5 μm or less, and it is composed of inorganic materials.
[0011] It is particularly preferable that the vinyl group is directly bonded to a silicon atom.
[0012] The present invention's method for producing particle materials, having the above configuration, makes it possible to produce particle materials that are metal oxide particle materials with particularly high dispersibility in organic solvents. Furthermore, the present invention provides particle materials that are metal oxide particle materials with particularly high dispersibility in organic solvents, having the above configuration.
[0013] The particle material and its manufacturing method of the present invention will be described in detail below based on the following embodiments.
[0014] Here, the numerical values described herein can be used to define a range in which those values are used as upper or lower limits when making corrections, and that range may or may not include those values. Furthermore, the numerical range "x to y" described herein includes the lower limit x and the upper limit y. New numerical ranges can be constructed by arbitrarily combining these upper and lower limits, as well as the numerical values listed in the specification or examples. The new numerical range may also be a range that does not include one or both of the upper and lower limits. For example, a range greater than x can be adopted, or a range less than y can be adopted. Furthermore, numerical values arbitrarily selected from any of the above numerical ranges can be used as the upper and lower limits of the new numerical range. (Particle Material) The particle material of this embodiment is composed of an inorganic material. The inorganic material is not particularly limited, but examples include silica, alumina, zirconia, titania, and composite oxides of these metal oxides. Examples of composite oxides include calcium titanate, barium titanate, and zeolite.
[0015] The particle material of this embodiment has a volume-average particle size of 0.1 μm or more and 5 μm or less. Examples of upper limits include 4 μm, 3 μm, and 2 μm, and examples of lower limits include 0.15 μm, 0.18 μm, and 0.20 μm. These upper and lower limits can be combined arbitrarily.
[0016] Furthermore, it is preferable that D90 / D10 be between 1.5 and 10, with examples of lower limits being 2.0, 2.5, and 3.0, and examples of upper limits being 9, 8, and 7. A certain degree of variation in the particle size of the particle material improves the fluidity of the particle material itself and the fluidity of the resin composition formed by dispersing it in the resin material. To increase D90 / D10, this can be achieved by adding particles that are larger or smaller than the volume-average particle size to the raw particle material used when manufacturing the particle material of this embodiment using the method described later, or by employing the VMC method (a method of manufacturing particle material made of metal oxides by deflagrating a metal particle material in a high-temperature oxidizing atmosphere and then rapidly cooling it).
[0017] Furthermore, it is desirable that the particle material of this embodiment has a low degree of aggregation, specifically that D100 is 800 μm or less.
[0018] In this embodiment, the particle material is obtained by dispersing 10 g of powder in 40 g of toluene using ultrasound for 30 minutes, and then letting it stand in a 110 mL glass bottle for 30 minutes, resulting in a supernatant of less than 20 mm.
[0019] The particle material of this embodiment preferably has a sphericity of 0.8 or higher, and more preferable lower limits include 0.85, 0.9, 0.95, and 0.99. Sphericity is determined by taking a picture with a SEM and using the area and perimeter of the observed particle, as follows: (Sphericity) = {4π × (Area) ÷ (Perimeter)} ２ The value is calculated using the formula}. The closer to 1, the closer it is to a perfect sphere. Specifically, the average value measured for 100 particles using image analysis software (Asahi Kasei Engineering Co., Ltd.: A-Image-kun) is adopted.
[0020] The particle material of this embodiment is surface-treated with a surface treatment agent. The surface treatment agent is not particularly limited. Preferred surface treatment agents are those having carbon-containing functional groups such as phenyl groups, alkyl groups, vinyl groups, epoxy groups, methacrylic groups, amino groups, and isocyanate groups. These functional groups are introduced by the surface treatment. It is preferable to use silane compounds or silazanes as surface treatment agents. Furthermore, it is preferable that the vinyl group is directly bonded to the silicon atom, and in order to realize such a configuration, the surface treatment agent is preferably one that has a vinyl group, and vinyltrimethoxysilane is particularly preferred.
[0021] For surface treatment, a surface treatment agent such as a silane compound can be directly brought into contact with the surface of the particle material, or a solution can be prepared using a solvent (e.g., water) and brought into contact with the surface. After that, the material can be left to stand or heated until the reaction is complete. Further details will be explained in the section on the manufacturing method of the particle material below.
[0022] Furthermore, the amount of surface treatment to be performed is the surface area H(m²) per gram. ２The C / H value calculated from the specific surface area (H) and carbon content (C) (mass%) is 0.015 or more and 0.045 or less, preferably 0.020 or more and 0.035 or less. By setting the C / H value above the lower limit, dispersibility in organic solvents such as toluene can be improved, and by setting it below the upper limit, aggregation of the particle material can be suppressed. Here, the specific surface area (H) is a value measured by the BET method using nitrogen gas. The carbon content is calculated from the amount of carbon dioxide generated by oxidizing the sample.
[0023] The value of the cleaning C / H ratio, calculated from the amount of carbon after cleaning (cleaning C: mass%), is preferably 0.013 to 0.032, and more preferably 0.018 to 0.030. In other words, it is preferable that the carbon present on the surface of the particle material is in a state where it is not easily removed by cleaning, that is, it is bonded to the surface by strong bonds such as covalent bonds. By setting the cleaning C / H value above the lower limit, the dispersibility in organic solvents such as toluene can be improved, and by setting it below the upper limit, the aggregation of the particle material can be suppressed. Here, the cleaning conditions are as follows: 5 g of the particle material is placed in 35 mL of methyl ethyl ketone (MEK) and ultrasonic waves are applied for 5 minutes to clean it. In this specification, the ultrasonic irradiation conditions are 38 kHz and 300 W.
[0024] When introducing functional groups using silane compounds, it is assumed that they will react and bond with OH groups present on the surface of the inorganic material constituting the particle material. Preferably, 50% or more of the OH groups disappear as a result of the reaction, more preferably 70% or more, even more preferably 90% or more, and particularly preferably 100%. (Method for manufacturing particle material) The method for manufacturing the particle material of this embodiment comprises a surface treatment step and other necessary steps. The method for manufacturing the particle material of this embodiment is a manufacturing method that can suitably produce the particle material of this embodiment described above. ・Surface treatment step The surface treatment step is a step of performing a surface treatment on the raw particle material to obtain a treated particle material. The raw particle material is composed of an inorganic material. Regarding the inorganic material constituting the raw particle material, the particle size distribution of the raw particle material, and the sphericity, the same as those described in the particle material of this embodiment described above can be used, so further explanation is omitted.
[0025] Surface treatment is a process of surface-treating raw material particles with a surface treatment agent composition. The surface treatment agent composition is a mixture of the surface treatment agent and water. Since the surface treatment agent contains a silane compound having an alkoxy group, which is a hydrolyzable functional group, a certain amount of hydrolysis can be expected to proceed to some extent by being present with a certain amount of water, and an appropriate surface treatment reaction can be expected. Furthermore, it is preferable that the boiling point of the surface treatment agent is 200°C or lower. Examples of surface treatment agents include silane compounds having one or two vinyl groups, phenyl groups, alkyl groups, epoxy groups, phenylamino groups, etc. as functional groups, and two to three alkoxy groups such as methoxy groups. It is preferable that the surface treatment agent has a vinyl group as a functional group, and vinyltrimethoxysilane is particularly preferred as the surface treatment agent. Among the silane compounds having a vinyl group, vinyltrimethoxysilane is the compound with the fewest carbon atoms and the smallest molecular weight, and is preferred because it is highly reactive and inexpensive. However, because vinyltrimethoxysilane has a small molecular weight, it is highly volatile, and by mixing it with water in the surface treatment agent composition and performing hydrolysis beforehand, the volatility can be suppressed and the stability of the surface treatment agent can be increased.
[0026] The water content of the surface treatment agent composition is between 4% and 10% based on the mass of the surface treatment agent. Examples of lower limits include 4.5%, 4.75%, and 5%, while examples of upper limits include 9%, 8%, 7%, 6%, 5.5%, and 5%. If the water content exceeds or is above the lower limit, the reactivity of the surface treatment agent can be fully exhibited and aggregation can be suppressed. Therefore, if the water content is below or below the upper limit, dispersibility in organic solvents can be improved.
[0027] Furthermore, when performing surface treatment with a surface treatment agent composition, the amount of methanol in the surface treatment agent composition is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. Silane compounds undergo hydrolysis when they react with water. In particular, when the silane compound has a methoxy group, the amount of methanol produced by hydrolysis increases as the amount of water increases or as the reaction with water progresses. Methanol has low affinity for toluene and is present on the surface of the particle material, so as the amount of methanol increases, the dispersibility of the particle material in toluene decreases. In other words, by controlling the amount of methanol produced after adding water to the surface treatment agent to within these ranges, aggregation of the particle material can be suppressed when 10 g of powder is dispersed in 40 g of toluene with ultrasound for 30 minutes.
[0028] The amount of surface treatment agent composition to be reacted is set so that the C / H value described above is 0.015 or more and 0.045 or less, and the cleaning C / H value described above is 0.013 or more and 0.032 or less. Preferably, the C / H and cleaning C / H values are within the range described for the particle material of this embodiment. Increasing the amount of surface treatment agent composition increases the C and cleaning C values, and increasing the reactivity of the surface treatment agent composition increases the cleaning C value.
[0029] Furthermore, the conditions for reacting the surface treatment agent composition are such that the moisture content in the treated particle material after surface treatment is greater than 0 ppm and greater than 400 ppm, with examples of lower limits being 50 ppm and 100 ppm, and examples of upper limits being 350 ppm and 300 ppm. If the moisture content is greater than or equal to the lower limit, the reactivity of the surface treatment agent can be fully exhibited and aggregation can be suppressed, so if it is kept below the upper limit, dispersibility in organic solvents can be improved. The reaction can be completed by heating after contacting the raw material particle material with the surface treatment agent composition. There are no particular limitations on the heating temperature, but examples of lower limits being room temperature, 40°C, 60°C, 80°C, 100°C, 120°C, 140°C, etc. ・Other steps As other steps, after the surface treatment step, there may be a classification step in which coarse particles of a predetermined particle size or larger are classified and removed. The classification step may be carried out by either a dry or wet method, and examples of methods include using a sieve or using gravity such as centrifugal classification.
[0030] Furthermore, as a method for producing raw material particle materials, there is the deflagration method (VMC method), which is obtained by deflagrating metal particle materials made of metal in a high-temperature oxidizing atmosphere and then rapidly cooling them, and the raw material particle materials can be prepared by pulverizing the inorganic materials constituting the raw material particle materials, then melting them in a high-temperature atmosphere and then rapidly cooling them (melting method). (Slurry composition) A slurry composition can be formed by dispersing the particle materials of this embodiment described above in a dispersion medium. The particle materials of this embodiment can be dispersed in a resin material and used as a resin composition for semiconductor materials, etc., but in order to disperse them in the resin material when forming the resin composition, a slurry composition dispersed in a dispersion medium made of an organic solvent may be used as a step.
[0031] For example, when attempting to disperse a particulate material in a highly hydrophobic resin material, a slurry composition using a highly hydrophobic organic solvent such as toluene as the dispersion medium can be employed.
[0032] The surface-modified particle material and slurry composition of the present invention will be described in detail below based on the following examples. (Example 1) 1 part by mass of the surface treatment agent composition was added to 100 parts by mass of a particle material formed from silica (sphericity 0.9 or higher, volume average particle size 0.53 μm, manufactured by Admatex: SC2500-SQ), and stirring was continued for 2 minutes. After that, the surface treatment was completed by standing at 40°C for 8 hours, and this was used as the test sample for this example. The surface treatment agent composition was prepared by adding 5 parts by mass of water to 100 parts by mass of vinyltrimethoxysilane (boiling point 148°C) as a surface treatment agent. As a result, the water content of the surface-treated silica was 203 ppm. (Example 2) 1 part by mass of the surface treatment agent composition was added to 100 parts by mass of a particle material formed from silica (sphericity 0.9 or higher, volume average particle size 2.2 μm), and stirring was continued for 2 minutes. After that, the surface treatment was completed by standing at 40°C for 8 hours, and this was used as the test sample for this example. The surface treatment agent composition was prepared by adding 5 parts by mass of water to 100 parts by mass of vinyltrimethoxysilane. As a result, the moisture content of the surface-treated silica was 212 ppm. (Example 3) 1 part by mass of the surface treatment agent composition was added to 100 parts by mass of silica-formed particle material (sphericity 0.9 or higher, volume average particle size 0.31 μm), and stirring was continued for 2 minutes. After that, the surface treatment was completed by standing at 40°C for 8 hours, and this was used as the test sample for this example. The surface treatment agent composition was prepared by adding 5 parts by mass of water to 100 parts by mass of vinyltrimethoxysilane. As a result, the moisture content of the surface-treated silica was 312 ppm. (Comparative Example 1) The test sample for this comparative example was prepared in the same manner as in Test Example 1, except that the amount of water added when preparing the surface treatment agent composition was changed to 0 parts by mass. The moisture content of the surface-treated silica was 270 ppm. (Comparative Example 2) The test sample for this comparative example was prepared in the same manner as in Test Example 1, except that the amount of water added when preparing the surface treatment agent composition was changed to 35 parts by mass. The moisture content of the surface-treated silica was 432 ppm. (Comparative Example 3) The test sample for this comparative example was prepared in the same manner as in Test Example 1, except that vinyltrimethoxysilane as the surface treatment agent was changed to octenyltrimethoxysilane (boiling point 232°C). In octenyltrimethoxysilane, the vinyl group is bonded to the silicon atom via hexamethylene.The moisture content of the surface-treated silica was 214 ppm.
[0033] (Evaluation) For the test samples in this test example, the specific surface area (H:m²) was determined by the BET method using nitrogen gas. ２ The following parameters were measured: carbon content (C: mass%), carbon content after washing (washing C: mass%), moisture content (Karl Fischer method), and particle size distribution in the dry state (laser diffraction particle size distribution analyzer). In addition, A (moles of functional groups per 100 g of particle material after washing: theoretically calculated from the carbon content after washing and the molecular weight of the functional groups calculated from the surface treatment agent), C / H, washing C / H, and D100 (particle size when the volume of the particles is accumulated from the smallest particle size to 100%) were calculated. Furthermore, the dispersibility in toluene was evaluated using the above method. Dispersibility was evaluated as excellent when the supernatant was 20 mm or less using the above method. Regarding cost, trimethoxysilane (KBM-1003) was evaluated as inexpensive and low-cost. Octenyltrimethoxysilane (KBM-1083) was evaluated as expensive and high-cost. These evaluation results are shown in Table 1. As is clear from Table 1, in Examples 1 to 3, the generation of aggregated particles of D100 ranging from 95 μm to 121 μm was small, indicating excellent dispersibility.
[0034] In contrast, the test sample of Comparative Example 1 had a C / H ratio of 0.014, less than 0.015, and a post-wash C / H ratio of 0.12, less than 0.13, indicating insufficient dispersibility due to the small amount of functional groups on the surface. The absolute amount of carbon was 0.084%, which is less than the absolute amount of carbon in Example 1, where the only difference was the presence or absence of water in the surface treatment agent composition (174%). This resulted in a smaller amount of surface treatment agent remaining on the surface. It was found that adding water to form the surface treatment agent composition, as in Example 1, suppresses volatility and increases the amount of surface treatment agent that reacts with the surface of the particle material.
[0035] In the test sample of Comparative Example 2, it was found that the high water content of the surface treatment agent composition led to the aggregation of the particle material, resulting in D100 exceeding 800 μm, reaching 825 μm.
[0036] In the test sample of Comparative Example 3, a surface treatment agent with a higher molecular weight (especially the molecular weight of the functional group), which is more expensive, was used, resulting in a C / H ratio of 0.046, which is greater than 0.045, and a cleaning C / H ratio of 0.033, which is greater than 0.032. In other words, by checking the C / H ratio and cleaning C / H ratio, it was found that a surface treatment agent with a high molecular weight and therefore presumably more expensive was being used.
Claims
1. The process includes a surface treatment step in which a raw material particle material composed of inorganic materials is surface-treated using a surface treatment agent composition containing a silane compound and water to obtain a treated particle material, wherein the treated particle material contains more than 0 ppm and 400 ppm or less of water based on the total mass, and the amount of the surface treatment agent composition and the surface treatment conditions in the surface treatment step are as follows: Surface area H (m²) per gram ２ A method for producing particle material, wherein the C / H value calculated from the carbon content C (mass%) is 0.015 or more and 0.045 or less, the C / H value after washing the treated particle material is 0.013 or more and 0.032 or less, the theoretical number of moles of functional groups A (mol / 100g) / H calculated from the C of the treated particle material after washing is 0.0003 or more, and the D100 in the particle size distribution measured by dry method is 800 μm or less.
2. The method for producing a particle material according to claim 1, wherein the surface treatment agent is vinyltrimethoxysilane.
3. The method for producing a particle material according to claim 1 or 2, wherein the raw material particle material is a metal oxide obtained by deflagrating a metal particle material made of metal in a high-temperature oxidizing atmosphere and then rapidly cooling it.
4. The method for producing particle material according to any one of claims 1 to 3, wherein the surface treatment agent has a methoxy group, and the surface treatment agent composition is mixed with 4% by mass or more of water based on the mass of the surface treatment agent, and then brought into contact with the raw material particle material in the surface treatment step before the methanol content exceeds 5% by mass based on the total mass of the surface treatment agent composition.
5. A method for producing a particle material according to any one of claims 1 to 4, further comprising a classification step of classifying and removing coarse particles of a predetermined particle size or larger after the surface treatment step.
6. Surface area H (m²) per gram ２ The particle material is composed of inorganic materials and has a C / H value calculated from the carbon content C (mass%) of 0.015 to 0.045, a C / H value after washing of 0.013 to 0.032, a theoretical number of moles of functional groups A (mol / 100g) / H calculated from the C after washing of 0.0003 or more, contains moisture of more than 0 ppm and less than 400 ppm based on the total mass, has a D100 in the particle size distribution measured by dry method of 800 μm or less, is surface-treated so that when 10 g of powder is dispersed in 40 g of toluene with ultrasound for 30 minutes and left to stand in a 110 mL glass bottle for 30 minutes, the supernatant is less than 20 mm, has a volume average particle size of 0.1 μm or more and less than 5 μm.
7. The particle material according to claim 6, having a vinyl group directly bonded to a silicon atom.