WO2023175994A1 - Matériau particulaire inorganique creux, sa méthode de production, charge inorganique, composition de suspension et composition de résine - Google Patents

Matériau particulaire inorganique creux, sa méthode de production, charge inorganique, composition de suspension et composition de résine Download PDF

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WO2023175994A1
WO2023175994A1 PCT/JP2022/012924 JP2022012924W WO2023175994A1 WO 2023175994 A1 WO2023175994 A1 WO 2023175994A1 JP 2022012924 W JP2022012924 W JP 2022012924W WO 2023175994 A1 WO2023175994 A1 WO 2023175994A1
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inorganic particle
hollow inorganic
particle material
core
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PCT/JP2022/012924
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English (en)
Japanese (ja)
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守 山西
雄己 新井
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株式会社アドマテックス
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Priority to PCT/JP2022/012924 priority Critical patent/WO2023175994A1/fr
Priority to TW112109927A priority patent/TW202402670A/zh
Publication of WO2023175994A1 publication Critical patent/WO2023175994A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid

Definitions

  • the present invention relates to a hollow inorganic particle material, a method for producing the same, an inorganic filler, a slurry composition, and a resin composition.
  • hollow inorganic particle materials with increased porosity in order to lower the relative permittivity and dielectric loss tangent to the required levels. These generally have poor mechanical properties, crack during kneading during resin composition production, and as a result, some do not maintain the expected hollow structure in the resin composition.
  • hollow silica has excellent performance
  • conventional manufacturing methods require the use of toxic compounds in the reaction as essential materials, making production management difficult and requiring special equipment.
  • toxic compounds in the reaction are many things that are difficult to manufacture on an industrial scale, and things that are theoretically difficult to scale up.
  • it is expected that a method that can be mass-produced through simpler steps will be provided.
  • the present invention has been made in view of the above-mentioned problems, and is a new hollow inorganic material having sufficiently small dielectric constant and dielectric loss tangent, and having ionic impurities as low as silica filler for electronic materials having a solid structure.
  • the problem to be solved is to provide particulate materials.
  • Hollow inorganic particle materials are manufactured by "template synthesis" in most cases. That is, after silica is deposited and polymerized on the outside or inside of a template (mold) having a shape close to the target particle shape, the template is removed.
  • templates Various methods are known for making templates, and they can be roughly divided into those that form a silica layer on the outer shell of a core material depending on the size of the void, and those that use core-shell particles as a precursor, and those that use W phase of O/W/O type micelles.
  • the most commonly used method is to use core-shell particles as a precursor.
  • the hollow inorganic particle material of the present invention can also be said to be produced by template synthesis using core-shell particles as a precursor.
  • the Stober method in which orthosilicate esters such as tetraethoxysilane (TEOS) and tetramethoxysilane (TMOS) are hydrolyzed with a base catalyst, is often applied mutatis mutandis.
  • TEOS tetraethoxysilane
  • TMOS tetramethoxysilane
  • a shell layer thickness of 24 nm is achieved by adding TMOS in an amount of 80 mmol/L over about 6 hours.
  • the shell layer of the hollow particles in the present invention is derived from a silica structure having a three-dimensional regular structure.
  • This silica structure has a structure in which silica is arranged in a structure corresponding to the microphase separation structure of a surfactant described in the embodiment section. Specifically, it has a three-dimensional lamellar structure called an L3 phase (or sponge phase) or a bicontinuous cubic phase (or gyroid phase). This structure is due to self-organization of the surfactant, and which structure it forms is determined by the concentration (initial concentration) and temperature.
  • Patent Documents 9 and 10 and Non-Patent Document 2 disclose techniques for synthesizing silica particles having mesopores from this phase-separated structure.
  • the thickness of the shell layer can be increased without the need to add unnecessary catalysts, and it is also possible to form a shell layer with a constant thickness. He discovered that this could be the case and completed the following invention.
  • the method for producing a hollow inorganic particle material of the present invention that solves the above problems involves dispersing a core material in a mother liquor that is a mixture of a nonionic surfactant and a dispersion medium that contains water and may contain an aqueous solvent. a core material dispersion preparation step of preparing a core material dispersion;
  • a core-shell complex forming step of performing a polycondensation reaction of the hydrolyzate of the adsorption complex in the mother liquor to obtain a core-shell complex; a firing step of firing the core-shell composite to remove the core material; has.
  • the hollow inorganic particle material of the present invention that solves the above problems is a material that can be produced by the method for producing a hollow inorganic particle material of the present invention, and has a hollowness ratio of 20 volume % or more and 75 volume % or less, and is an inorganic material.
  • the shell layer has a structure derived from a microphase separation structure.
  • the shell layer has a structure derived from a microphase-separated structure
  • a structure derived from a microphase-separated structure which is a three-dimensional lamellar structure called an L3 phase (or sponge phase) or a bicontinuous cubic phase (or gyroid phase).
  • L3 phase or sponge phase
  • a bicontinuous cubic phase or gyroid phase.
  • the microphase-separated structure in this specification has a three-dimensional network structure in which rod-shaped micelles with diameters ranging from 1 nm to 8 nm are connected three-dimensionally when viewed locally, and multiple networks penetrate each other. It refers to the structure that
  • a method to determine whether the shell layer has a structure derived from a microphase separation structure is to examine the surface, fractured surface, or cut end surface of the shell layer using a transmission electron microscope (TEM) or a scanning transmission electron microscope. (STEM) or scanning electron microscope (SEM). Specifically, minute changes in silica density appear as patterns originating from the microphase-separated structure. In particular, it is preferable that 50% or more of the volume of the shell layer has a structure derived from a microphase separation structure.
  • the microphase separation structure is preferably a sponge structure.
  • Another hollow inorganic particle material of the present invention that solves the above problems is a hollow inorganic particle material having a hollowness ratio of 20 volume % or more and 75 volume % or less and having a shell layer made of an inorganic material,
  • the inorganic material contains 90% or more silica based on the mass of the entire particulate material,
  • the content of alkali metals, alkaline earth metals, halogens, and oxoacids is all 10 ppm or less based on the mass of the entire particle material,
  • the volume average particle diameter of the primary particles is 100 nm or more and 5 ⁇ m or less.
  • the present invention has a shell layer made of dense silica, has a sufficiently small dielectric constant and dielectric loss tangent, and has a sufficiently small dielectric constant and dielectric loss tangent, and is free from ionic impurities. It is possible to provide a hollow inorganic particle material that has a solid structure and has a low cost comparable to that of silica filler for electronic materials. According to the present invention, it is possible to provide hollow inorganic particle materials that are difficult to penetrate into resins and solvents when processed into electronic materials and can exhibit excellent low dielectric constant and low dielectric loss tangent even in resin compositions.
  • inorganic particle with internal voids it can have the same structure as a normal inorganic particle material without internal voids (solid particle material), so compared to solid particle materials, varnish Or, there is no extreme increase in viscosity when processed as a resin masterbatch, and it can be used as a hollow particle material as it is, or as a resin composition dispersed in a resin material, or as a solid particle material or a resin composition using a solid particle material. It is also possible to provide equivalent handling properties.
  • 1 is a scanning electron microscope (SEM image) photograph of the hollow inorganic particle material obtained in Example 1.
  • 1 is a particle size distribution of the hollow inorganic particle material obtained in Example 1. This is an infrared absorption spectrum of the surface-treated hollow inorganic particle material obtained in Example 1.
  • 1 is a scanning electron microscope (SEM image) photograph of a cross section of a resin composition using the hollow inorganic particle material obtained in Example 1. These are the dielectric constant and thermal expansion coefficient of a resin composition using a mixture of the hollow inorganic particle material obtained in Example 1 and Comparative Example 1.
  • 2 is a scanning electron microscope (SEM image) photograph of the inorganic particle material obtained in Comparative Example 2.
  • 3 is a scanning electron microscope (SEM image) photograph of the inorganic particle material obtained in Comparative Example 3.
  • SEM scanning electron microscope
  • the hollow inorganic particle material of the present invention and its manufacturing method will be described in detail below based on embodiments.
  • the hollow inorganic particle material of this embodiment can be suitably used as an inorganic filler to be included in a resin composition for electronic materials.
  • a resin composition for electronic materials For example, it can be contained in a resin composition used for a substrate material, a resin composition used for a sealing material, a varnish, or a resin masterbatch.
  • it may be used as an inorganic filler by mixing with other inorganic particle materials.
  • Other inorganic particle materials can be mixed at a ratio of 50% or more and 800% or less based on the mass of the hollow inorganic particle material.
  • the hollow inorganic particle material of this embodiment includes a shell layer made of an inorganic material, and the shell layer defines voids therein.
  • the presence or absence of voids inside the shell layer of a hollow inorganic particle material can be determined by transmission electron microscopy (TEM) observation, scanning transmission electron microscopy (STEM) observation, or scanning This can be confirmed by electron microscopy (SEM) observation.
  • the hollowness in addition to observing the cut surface while the particle is embedded in resin, the hollowness can also be confirmed by an observation method that reflects the internal structure of the particle by increasing the acceleration voltage of the electron beam. can.
  • the hollowness ratio is the ratio of the volume of voids existing inside based on the volume of the hollow inorganic particle material. Unless specifically limited, the hollowness ratio is an average value of all the particles constituting the hollow inorganic particle material, and is calculated as a ratio of the sum of the volumes of voids based on the sum of the volumes of the hollow inorganic particle materials. The details are calculated using the method described later.
  • the relative dielectric constant required for the hollow inorganic particle material is essential to be 3.4 or less, preferably 3.0 or less, more preferably 2.8 or less, and even more preferably 2.5 or less.
  • the relative permittivity of silica, which constitutes the inorganic material is 3.6 to 4.2, and when combined with the relative permittivity of vacuum of 1.0, using the Maxwell-Garnett equation used to predict the permittivity of composite materials, Calculating the relative permittivity of hollow inorganic particle materials, the larger the hollow factor, the smaller the permittivity, and the hollow factors that give the relative permittivity of 3.4, 3.0, 2.8, and 2.5 are approximately 20%, 30%, 35%, 45%. Therefore, the lower limit of the porosity is at least 20%, preferably 30%, more preferably 35%, and still more preferably 45%.
  • the upper limit of the hollowness ratio is set to 75%, preferably 70%, and more preferably 65%. By keeping the value below this upper limit, sufficient mechanical strength can be obtained, which can effectively prevent damage when handling the hollow inorganic particle material or when mixing it with a resin material to form a resin composition. . Since the hollow inorganic particle material is not damaged, a sufficiently large void can be secured and the necessary electrical characteristics can be achieved.
  • lower limits of the thickness of the shell layer include 10 nm, 20 nm, 50 nm, and 100 nm, and upper limits include 300 nm, 200 nm, 150 nm, and 100 nm. These lower and upper limits are arbitrary. can be combined with
  • the inside of the particle has a region that is isolated from the outside of the particle by the shell layer through which molecules such as solvents and resins cannot pass.
  • the shell layer that partitions the voids may have so-called micropores, which are sufficiently small compared to the particle size, but there are holes (mesopores and macropores) that allow molecules of solvents, resins, etc. to pass through. must not.
  • Particles without voids are called solid silica particle materials.
  • the hollow inorganic particle material of this embodiment has one or more voids per particle.
  • the size of the voids is analyzed by measuring the true specific gravity using two types of probes (helium gas and nitrogen gas): one that passes through the micropores and one that does not.
  • Micropores are holes that allow only helium gas to pass through, but not nitrogen.
  • the density ⁇ shell of the shell layer is preferably 2.1 g/cm 3 or more and 2.5 g/cm 3 or less, more preferably 2.2 g/cm 3 or more and 2.4 g/cm 3 or less. .
  • the hollowness ratio can be calculated from the density ⁇ shell of the shell layer and the density ⁇ particle of the hollow inorganic particle material. Specifically, the hollowness ratio can be calculated as ⁇ 1- ⁇ N2 / ⁇ He ⁇ 100 (%) (calculation method 1). Further, the hollowness ratio can be calculated from (1-2t/D) 3 ⁇ 100 (%) by determining the particle diameter (D) and the shell layer thickness (t) from a TEM image or a SEM image (calculation method 2). Calculation method 2 uses the average value of the measured values of 1,000 or more hollow inorganic particle materials for particles that can be identified on the image, unless it is necessary to calculate the hollowness ratio of individual particles. do.
  • Calculation method 1 is used to measure the hollowness ratio when 1 g or more of hollow inorganic particle material can be measured independently.
  • Calculation method 2 is adopted when the value of the hollowness ratio for each particle of the hollow inorganic particle material is required.
  • Calculation method 2 is adopted when the hollow inorganic particle material to be measured is filled in a resin composition, when there is less than 1 g of the sample, or when calculation method 1 cannot be adopted.
  • the volume average particle size of the primary particles is 100 nm or more and 5 ⁇ m or less.
  • Examples of the lower limit of the volume average particle diameter of the primary particles are 100 nm, 120 nm, and 150 nm, and the upper limits are 5 ⁇ m, 3 ⁇ m, 2 ⁇ m, and 1 ⁇ m. These lower limit values and upper limit values can be arbitrarily combined.
  • the shell layer is composed of an inorganic material, it may also contain an unavoidably mixed organic material.
  • the inorganic material contains 90% by mass or more of silica.
  • the proportion of silica in the inorganic material is preferably 95% by mass or more, more preferably 98% by mass or more, and even more preferably 99% by mass or more.
  • Inorganic materials that can be included other than silica include, but are not particularly limited to, metal oxides such as alumina, zirconia, and titania, metal nitrides, and oxoacids such as boric acid.
  • Na, Mg, Al, P, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Sb, B, and V are listed.
  • the content of each of the 19 elements is 100 ppm or less, preferably 50 ppm or less, more preferably 20 ppm or less, still more preferably 10 ppm or less.
  • the content of cations and anions is each 10 ppm or less, preferably 5 ppm or less, more preferably 2 ppm or less, still more preferably 1 ppm or less.
  • the amount of inorganic components other than silicon By keeping the amount of inorganic components other than silicon below this upper limit, it is possible to reduce ionic impurities extracted from the hollow inorganic particle material of this embodiment.
  • the insulation properties can be improved, and by keeping the amount of halogen ions below this upper limit, the hollow inorganic particle material of this embodiment can be improved.
  • it When used as a filler for electronic materials, it can sufficiently suppress the occurrence of wiring corrosion due to halogen infiltration/diffusion into the product, and by keeping the amount of oxoacid ions below this upper limit, free oxoacid ions can be suppressed. It becomes possible to sufficiently reduce the amount of oxoacid that exists as an acid and does not constitute a shell layer as a composite oxide, and thus insulation and corrosion properties can be improved.
  • the contents of uranium (U) and thorium (Th) are each 5 ppb or less, preferably 3 ppb or less, more preferably 2 ppb or less, and still more preferably 1.5 ppb or less.
  • the hollow inorganic particle material of this embodiment when used as a filler for electronic materials, semiconductor device malfunctions (soft errors) due to alpha rays generated within the product can be prevented. It is possible to reduce this to a level that cannot be distinguished from soft errors caused by alpha rays or cosmic radiation caused by other components.
  • -Surface area and dielectric properties of hollow inorganic particle materials The dielectric constant has been described above, but when considering the use of the hollow inorganic particles according to the present invention, the dielectric loss tangent must also be sufficiently low.
  • the dielectric loss tangent is evaluated in the composite material originally used, but as a single hollow inorganic particle material, it is desired to be 0.01 or less, preferably 0.005 or less, and 0.003 or less. More preferably, it is 0.002 or less.
  • silanol exists at grain boundaries and surfaces of silicon dioxide, which causes deterioration of dielectric properties.
  • the dielectric loss tangent to the filler be 0.01 or less.
  • the upper limit of index F was set to the condition that the maximum particle diameter (providing the minimum specific surface area) of 2 ⁇ m was achieved. Specifically, since the specific surface area of solid silica is theoretically about 1.5 m 2 /g, 7 ⁇ 10 -3 g/m 2 is set as the upper limit of the index F. did.
  • -Surface treatment of hollow inorganic particle material The hollow inorganic particle material of this embodiment can be subjected to surface treatment. Surface treatment can be expected to improve dielectric properties and improve compatibility with other materials.
  • the first purpose is to eliminate silanol groups remaining on the surface of the hollow inorganic particle material by so-called capping.
  • examples of the surface treatment agent include those having a trimethylsilyl group, more specifically methoxytrimethylsilane and hexamethyldisilazane (HMDS).
  • a surface treatment agent can be used that can improve the affinity with the materials that will ultimately come into contact with it.
  • a silane compound can be employed as a surface treatment agent.
  • the silane compound include those having functional groups such as alkyl groups, vinyl groups, phenyl groups, methacrylic groups, epoxy groups, and alkyl groups having these groups in their side chains.
  • examples include, but are not limited to, methyltrialkoxysilane, dimethyldialkoxysilane, phenyltrialkoxysilane, dialkoxydiphenylsilane, n-propyltrialkoxysilane, hexyltrialkoxysilane, and octyltrialkoxysilane.
  • the manufacturing method of the hollow inorganic particle material of the present embodiment is a manufacturing method that can suitably manufacture the hollow inorganic particle material of the present embodiment described above, and uses core-shell particles having a core material as a core and silica as a shell as a precursor, This is a method for producing hollow inorganic particle materials by removing the core from the precursor and taking out the shell.
  • the method for producing a hollow inorganic particle material includes a core material dispersion preparation step, a composite forming step, a core shell composite forming step, a firing step, and other necessary steps.
  • the core material dispersion preparation step is a step of preparing a core material dispersion by dispersing the core material in a mother liquor.
  • the mother liquor is a mixture of a surfactant, a dispersion medium, and optionally a catalyst (typically, but not limited to, an acid or an alkali) to promote the polymerization of the silica.
  • the core material may be dispersed after the mother liquor is prepared, or the core material may be dispersed during the preparation of the mother liquor.
  • the order in which the surfactant, core material, and dispersion medium are mixed is not particularly limited.
  • a catalyst that promotes the polymerization of silica it may be added at the time of making the mother liquor, after making the mother liquor, at the same time as the addition of the hydrolyzable silane compound, or at the same time as adding the hydrolyzable silane compound. You can also do this after the addition is complete.
  • the surfactant has a three-dimensional lamellar structure (hereinafter abbreviated as "microphase separation structure") such as the L3 phase (or sponge phase) or bicontinuous cubic phase (or gyroid phase). ) and become adsorbed on the surface of the core material.
  • microphase separation structure such as the L3 phase (or sponge phase) or bicontinuous cubic phase (or gyroid phase).
  • the surfactant used in the production method of the present invention is a nonionic surfactant (nonionic surfactant) that forms a microphase-separated structure in an appropriate temperature range and concentration range when dissolved in water. There are no particular restrictions on what you can get. Furthermore, such nonionic surfactants may be used alone or in combination of two or more types. Details of the nonionic surfactant will be described later.
  • the dispersion medium may be either water or an aqueous solvent containing water as a main component as described below.
  • Aqueous solvents are solvents that are miscible with water, including monoalcohols with 1 to 3 carbon atoms (methanol, ethanol, 1-propanol, 2-propanol), dialcohols (ethylene glycol, 1,2-propylene glycol, 1, 3-propylene glycol) and trial alcohol (glycerol), and a mixture of two or more may be used.
  • the concentration of the surfactant is such that a microphase-separated structure is formed.
  • the possible structures of surfactants in water vary from surfactant to surfactant as a function of temperature and concentration. Therefore, the optimum temperature and concentration must be determined experimentally for each surfactant.
  • the optimal conditions for the Pluronic surfactant (POE-POP block copolymer) L-64 were 1% by mass to 20% by mass at 40°C.
  • - Core material By selecting the core material, it is possible to synthesize hollow inorganic particle materials of various sizes. A void is formed having a size and shape that correlates to the size and shape of the selected core material.
  • the core material is preferably a particulate material that is dispersed in water or is dispersible in water.
  • micelles or vesicles using a surfactant and optionally a hydrophobic liquid are suitable in terms of size and shape, but they are difficult to form when the reaction to form silica around the core material proceeds. Since it is difficult to maintain the shape, it is preferable to use a core material made of particulate members.
  • the core material is preferably made of an organic material that is easy to remove, and is particularly preferably made of a resin material. It is preferable that the core material is made of a resin material and that the core material made of the resin material is removed by firing.
  • the core material may be a resin dispersed in water, such as a resin emulsion.
  • Non-Patent Document 3 in order to create core-shell particles with the desired structure, it is necessary to carefully select the size and charge of the core material.
  • the size of the core material must be larger than the silica nucleus (the smallest unit of silica). This is because large objects tend to gather in the center due to differences in convection speed.
  • the minimum unit of the microphase-separated structure containing silicic acid oligomers between lamellar layers (the silica core of this embodiment) used in the reaction of this embodiment is approximately 10 nm or less, and a core material with a larger size is not used.
  • the particles of a typical resin emulsion are preferably larger than 50 nm.
  • silica nuclei are weakly negatively charged. For this reason, if a material other than particles that are strongly negatively charged under the reaction conditions that generate silica nuclei is used as the core material, the repulsion between the surroundings of the core material and the generated silica nuclei will be reduced, and the surroundings of the core material will be A shell layer made of silica is formed in a suitable form.
  • the surface potential of the resin preferably used as the core material in the mother liquor is -3 mV or more, more preferably 3 mV or more. Resin emulsions having such characteristics may be synthesized by known methods, or commercially available products may be used.
  • the type of resin and the method of obtaining it are not limited.
  • the surfactant used in the method for producing hollow inorganic particle material of this embodiment will be explained.
  • the surfactant of this embodiment is a nonionic surfactant (nonionic surfactant), and when dissolved in water, forms a microphase-separated structure in an appropriate temperature range and concentration range.
  • Compounds with such characteristics have a polar block (A) and a non-polar block (B), and are classified according to the block configuration into AB type, which has two blocks, and ABA type, or BAB type, which has three blocks. (Many other types exist). There is no relationship between the block configuration and the formation of a microphase-separated structure.
  • the "size of the polar block (formula weight)" (M A ) and “the size of the nonpolar block (formula weight)” (M B ) must be approximately the same. . This is because when M A > M B , spherical micelles or cylindrical micelles are likely to be formed, and in the opposite case, so-called reverse micelles are likely to be formed.
  • A is often polyoxyethylene (POE, also called polyethylene oxide, polyethylene glycol, etc.)
  • B is polyoxypropylene (POP, also called polypropylene oxide, polypropylene glycol, etc.)
  • POP polyoxypropylene oxide, polypropylene glycol, etc.
  • Things with such a structure are not limited to the examples, but include POE-monoalkyl ether, POE-monoester (the above two-block type examples), POE-POP block copolymer, POE-diester ( Examples of the three-block type described above are listed.
  • POE-POP block copolymers are collectively referred to as Pluronic surfactants, and many products with different molecular weights and HLBs are commercially available under trademarks such as Pluronic, Poloxamer, and Pronon.
  • HLB is an abbreviation for Hydrophilic Lipophilic Balance, and in the Griffin method, it is an index defined as 20 ⁇ M A ⁇ (M A + M B ). The HLB values shown below are based on this definition.
  • M A is the formula weight of the A site (hydrophilic part) of the copolymer
  • M B is the formula weight of the B site (hydrophobic part) of the copolymer
  • (M A + M B ) is the formula weight of the entire copolymer.
  • the molecular weight is .
  • Silica grows on the A site of the block copolymer.
  • the ratio of A to the entire molecule is small, the density of the shell layer is low and many mesopores remain.
  • the proportion of A is large, the silica layer alone will stabilize, making it difficult for core-shell particles to grow.
  • the optimal range of HLB that was systematically determined for Pluronic surfactants was 6 or more and 14 or less. However, not all conditions having such conditions can be used in this embodiment. In other words, it is necessary to verify and optimize conditions such as whether a predetermined microphase separation structure is achieved, whether a composite can be formed, and whether a dense shell layer can be formed by denucleation by firing.
  • Pluronic type surfactants include, but are not limited to, Pluronic L-122, P-123, P-103, P-104, P-105, L-92, P-94, P-84, P-85, L-72, L-75, L-62, L-64, P-65, L-42, L-43, L-44, L-33, L-34, L-35, L- 23, 25R-2, 17R-2, 17R-3, 17R-4, etc.
  • equivalent and similar products to these products are sold by various companies.
  • Surfactants other than Pluronic type include, but are not limited to, POE-Solhytan fatty acid esters (for example, POE-Solhytan monooleate, POE-Solhytan monostearate, POE-Solhytan monooleate, POE POE-Solhit fatty acid esters (e.g., POE-Solhit monolaurate, POE-Solhit monooleate, POE-Solhit tantaoleate, POE-Solhit monostearate, etc.), POE-Solhit monostearate, etc.
  • POE-Solhytan fatty acid esters for example, POE-Solhytan monooleate, POE-Solhytan monostearate, POE-Solhytan monooleate, POE POE-Solhit fatty acid esters (e.g., POE-Solhit monolaurate, POE-Solhit
  • Fatty acid esters for example, POE-monooleate such as ⁇ , POE-quilycerin monostearate, POE-quilycerin monoisostearate, POE-quilycerin triisostearate, etc.
  • POE-fatty acid esters for example, ⁇ , POE-cystearate, POE- POE-alkyl ethers (e.g., POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-henyl ether, POE-2-octyl tether, POE-cholestanol ether) etc.).
  • nonionic surfactants for hollow particle synthesis
  • Patent Document 6 and Non-Patent Document 4 examples of using nonionic surfactants for hollow particle synthesis
  • their essential purposes are different.
  • the purpose is to generate swollen micelles, that is, oil-in-water emulsions, or to accumulate on the surface of oil droplets by making the B part of the surfactant molecule with silica adsorbed to the A part compatible with the oil droplet.
  • a shell layer made of silica is formed on the surface of the micelles.
  • the complex forming step is a step of mixing the core material dispersion with a hydrolyzate of hydrolyzable silane and stirring the mixture to form an adsorption complex in which the hydrolyzate is adsorbed on the surface of the core material.
  • the hydrolyzate of the hydrolyzable silane to be mixed can be added as a hydrolyzable silane and can be made into a hydrolyzate by allowing the hydrolysis reaction to proceed in the core material dispersion.
  • the generated hydrolyzate is adsorbed to the polar block A of the surfactant attached to the surface of the core material, and polymerized between the lamellar layers to form a silicic acid oligomer.
  • a silica surfactant complex using the microphase-separated structure as a template forms an adsorption complex in which the silica surfactant complex is accumulated on the surface of the core material.
  • hydrolyzable silanes include orthosilicate esters. Hydrolyzable silane becomes hydrolyzed by hydrolysis. Examples of commonly used orthosilicate esters include TEOS and TMOS.
  • TEOS and TMOS are oil-soluble, and if used as is, they will destroy the microphase separation structure of the surfactant.
  • the contact area with water is small, the portion that comes into contact with water is hydrolyzed extremely quickly, resulting in amorphous silica. For this reason, the yield of particles with hollow structures was extremely low.
  • Patent Document 10 and Non-Patent Document 5 an orthosilicate ester employing a group having a dialcohol or trialcohol in the side chain was used.
  • Such compounds have improved compatibility with water and can greatly reduce the reaction rate with water. Therefore, the yield of silica having the desired structure derived from the microphase-separated structure can be increased.
  • Examples of the orthosilicate ester having a group having a dialcohol or trialcohol in the side chain include a compound represented by Si(OR) 4 .
  • Each of the four R's can be independently determined, and at least one is a polyhydric alcohol residue, and the others may be an alkyl group.
  • the polyhydric alcohol residue is shown as the polyhydric alcohol with one hydroxyl group removed.
  • Such an orthosilicate ester can be prepared by a substitution reaction between a tetraalkoxysilane and a polyhydric alcohol, and the polyhydric alcohol residue of R varies depending on the type of polyhydric alcohol used, but for example, When ethylene glycol is used as the alcohol, R becomes -CH 2 CH 2 OH. Note that at least one of R may be a substituted polyhydric alcohol residue, and the others may be unsubstituted alkyl groups.
  • Examples of the polyhydric alcohol residue of R include ethylene glycol residue, diethylene glycol residue, triethylene glycol residue, tetraethylene glycol residue, polyethylene glycol residue, propylene glycol residue, dipropylene glycol residue, Polypropylene glycol residue, butylene glycol residue, hexylene glycol residue, glycerin residue, diglycerin residue, polyglycerin residue, neopentyl glycol residue, trimethylolpropane residue, pentaerythritol residue, maltitol residue
  • R1 is an ethylene glycol residue, a propylene glycol residue, a butylene glycol residue, or a glycerin residue.
  • TEOS can be synthesized by transesterification using an acid catalyst as disclosed in Patent Document 10 (proton type cation exchange resin) and Non-Patent Document 5 (hydrochloric acid). It can be synthesized using orthosilicate esters such as and TMOS and the above-mentioned polyhydric alcohols as raw materials.
  • orthosilicate esters such as and TMOS and the above-mentioned polyhydric alcohols as raw materials.
  • oxoacids such as boric acid, phosphoric acid, nitric acid, and sulfuric acid, or carboxylic acids such as acetic acid are suitable as acids used as catalysts. It is.
  • the core-shell composite forming step is a step in which a core-shell composite is obtained by causing a polycondensation reaction of the hydrolyzate present on the surface of the adsorption composite in the mother liquor.
  • a core-shell composite is one in which a shell (shell layer) made of a condensate of a hydrolyzate of a hydrolyzable silane is formed on the surface of a core material. Condensation of the hydrolyzate can be effectively advanced by heating after hydrolyzing the hydrolyzable silane. Further, if necessary, the reaction can be promoted by adding an acid or a base as a catalyst.
  • the firing step is a step in which the core-shell composite is fired to decompose and remove the surfactant contained in the core material and the shell layer. At the same time, the shell layer is densified.
  • the conditions are not particularly limited as long as the core material can be decomposed and removed and the shell layer formed on the surface of the core material is not destroyed, and examples include heating in an oxidizing atmosphere.
  • firing can be performed in the atmosphere at a temperature and for a time such that the core material is decomposed and removed. Examples of the firing temperature include 700°C or higher, 800°C or higher, 900°C or higher, 1000°C or higher, and 1100°C or higher.
  • the firing temperature be high, it should be lower than the temperature at which the silica constituting the hollow inorganic particle material aggregates or melts. Even in the case of agglomeration, if it can be separated into primary particles by a crushing operation, it may be agglomerated. Note that since the core-shell composite is manufactured while being immersed in the mother liquor, a step of separating it from the mother liquor can be performed before the core-shell composite is subjected to the firing process. For example, steps such as filtration, centrifugation, and drying can be employed.
  • the ratio of the amount of hydrolyzable silane/the amount of core material may be increased, or the core material with a high surface potential may be used.
  • a method using a surfactant having a high HLB and/or a high molecular weight can be adopted.
  • the size of the hollow inorganic particle material can be controlled by controlling the size of the core material, controlling the thickness of the shell layer, or a combination of these.
  • the slurry composition of this embodiment is a composition in which the hollow inorganic particle material of this embodiment described above is dispersed in a dispersion medium.
  • the slurry composition of this embodiment can be used for electronic materials such as semiconductor substrate materials, and is particularly preferably used for high frequency substrate materials.
  • the dispersion medium does not substantially contain water, and particularly preferably has a water content of 1000 ppm or less, more preferably 500 ppm or less.
  • the mixing ratio of the hollow inorganic particle material and the dispersion medium in the slurry composition is not particularly limited, it is preferable that the content of the hollow inorganic particle material is as large as possible.
  • the hollow inorganic particle material can be mixed until the viscosity reaches the maximum allowable in consideration of handleability.
  • (hollow inorganic particle material):(dispersion medium) can be mixed at a mass ratio of about 20:80 to 80:20.
  • the dispersion medium is not particularly limited, but includes organic solvents such as silicone oil, methyl ethyl ketone, alcohol, and hexane, and resin precursors such as epoxy resin precursors, polyester precursors, and silicone resin precursors.
  • organic solvents such as silicone oil, methyl ethyl ketone, alcohol, and hexane
  • resin precursors such as epoxy resin precursors, polyester precursors, and silicone resin precursors.
  • the hollow inorganic particle material is preferably surface-treated. In the surface treatment, it is preferable to introduce a functional group that can improve the affinity between the dispersion medium used and the other member with which the hollow inorganic particle material comes into contact when finally used.
  • the resin composition of this embodiment is a cured product made of the above-mentioned hollow inorganic particle material and a resin material in which the hollow inorganic particle material is dispersed.
  • the moisture content of the resin material is preferably 1000 ppm or less, more preferably 500 ppm or less.
  • the resin composition is preferably used for electronic materials, and as such electronic materials, it is preferably applied to those used for high frequency applications such as high frequency substrates. Since the hollow inorganic particle material of this embodiment has a low Df value, loss can be reduced even when used in applications where high frequency waves are transmitted.
  • the mixing ratio of the hollow inorganic particle material and the resin material in the resin composition is not particularly limited, it is preferable that the content of the hollow inorganic particle material is as large as possible.
  • the hollow inorganic particle material:resin material can be mixed at a mass ratio of about 10:90 to 90:10.
  • the resin material is not particularly limited, but general resin materials such as thermosetting resins (when mixed, it may be in either state before or after curing), thermoplastic resins, such as epoxy resins, melamine, etc. Examples include resin, acrylic resin, polycarbonate resin, polyester, silicone resin, liquid crystal polymer (LCP), polyimide, cyclic olefin polymer (COP), and polyphenylene oxide (PPO).
  • a single resin material can be used, or a plurality of types of resin materials can be mixed (alloyed, etc.) and used.
  • the moisture content of the resin material is preferably 1000 ppm or less, more preferably 500 ppm or less.
  • the hollow inorganic particle material is preferably surface-treated.
  • the hollow inorganic particle material of the present invention and the method for producing the same will be described in detail below based on Examples. (Analysis method) In this specification, each analysis is performed by the following method unless there is an explicit limitation.
  • Particle size distribution Optical particle size distribution measurement is the simplest method for analyzing the aggregation state of primary particles. On the other hand, since the refractive index of the hollow inorganic particles of the present invention is different from that of the inorganic material constituting them, the obtained average particle size shows a value that deviates from the true average particle size. Therefore, the aggregation state of particles is analyzed by optical particle size distribution measurement, and the average particle size is determined by image analysis.
  • Example cell 10cm 3 cells
  • Sample weight 1 to 3g
  • ⁇ Measurement gas helium and nitrogen
  • ⁇ Purge 10 times, 135kPa(G)
  • ⁇ Measurement 10 times, 135kPa(G)
  • the density ( ⁇ He ) when helium is used as the measurement gas represents the density of the shell layer.
  • the density ( ⁇ N2 ) when nitrogen is used represents the density of the hollow inorganic material. Therefore, the hollowness ratio was calculated as ⁇ 1 - ⁇ N2 / ⁇ He ⁇ 100 (%).
  • the hollow inorganic particle material of this embodiment was immersed in 50 g of pure water at a rate of 5 g, and heated in a closed container at 121° C. for 20 hours. The precipitate was removed by filtration to prepare extracted water. The ion concentration was determined by ion chromatography (Dionex, manufactured by Thermo Scientific) of the extracted water. Thirteen types of cations listed as F, Cl, NO 2 , Br, NO 3 , SO 4 , PO 4 , Li, Na, NH 4 , K, Mg, Ca, based on the mass of the immersed hollow inorganic particle material. and the anion content was calculated.
  • Dielectric properties For the dielectric properties of the powder, an 8 mm ⁇ x 30 mm PTFE tube filled with hollow inorganic particle material was used as a measurement sample, and an empty tube was used as a control sample. Each was placed in a cavity resonator connected to a network analyzer, and the resonant frequency and Q value in the 1 GHz band were determined. From these values, the complex permittivity was calculated using "Permittivity Calculation Application Using Perturbation Method" (Keycom Inc.).
  • Example 1 (Preparation of test sample) (Example 1) ⁇ Synthesis of hydrolyzable silane> 41 g of TEOS (JIS 1st grade), 60 g of propylene glycol (JIS 1st grade), and 5 mg of boric acid (JIS 1st grade) were placed in a flask and stirred at 80° C. for 24 hours. Ethanol was distilled off, and 65 g of orthosilicate ester (PGMS; Propylene-Grycol modified silane) having propylene glycol in its side chain was recovered. Although some amount of ethanol remained in this PGMS, it was used as it was for the synthesis of core-shell particles.
  • PGMS orthosilicate ester
  • ⁇ Synthesis of core-shell particles 6 g of acrylic resin (average particle size 300 nm, surface potential +52 mV) was mixed with 1000 g of a mother liquor consisting of 10% by mass of ABA block copolymer (HLB 7.9, average molecular weight 2900) and the balance water (core material dispersion). preparation process). Subsequently, 50 g of PGMS was stirred and mixed (complex formation step). The reaction mixture was kept at 40° C. for 36 hours to age the core/shell particles (core-shell composite formation step). The resulting solid was filtered under reduced pressure using filter paper (JIS 5A), and the precipitate was collected.
  • Example 2 A hollow inorganic particle material, which is a test sample of this example, was obtained by performing the same operation as in Example 1, except that the concentration of the ABA type block copolymer in the mother liquor was 5% by mass.
  • Example 3 A hollow inorganic particle material, which is a test sample of this example, was obtained by performing the same operation as in Example 1, except that the concentration of the POE-POP block copolymer in the mother liquor was 2% by mass.
  • Example 4 The same operation as in Example 1 was carried out, except that the mother liquor was prepared using another ABA type block copolymer (HLB 8.8, average molecular weight 1700) instead of the ABA type block copolymer used in Example 1.
  • HLB 8.8, average molecular weight 1700 ABA type block copolymer
  • Example 5 This experiment was carried out in the same manner as in Example 1, except that the mother liquor was prepared using a BAB block copolymer (HLB 8.0, average molecular weight 2700) instead of the ABA block copolymer used in Example 1.
  • Example Test samples of hollow inorganic particle materials were obtained.
  • Example 6 This experiment was carried out in the same manner as in Example 1, except that the mother liquor was prepared using an AB type surfactant (HLB 12.4, average molecular weight 500) instead of the ABA type block copolymer used in Example 1.
  • Example Test samples of hollow inorganic particle materials were obtained.
  • Example 7 This example was carried out in the same manner as in Example 4, except that 6 g of wax (average particle size 600 nm, surface potential +65 mV, solid content concentration 60%) was used instead of the acrylic resin used in Example 4. A test sample of hollow inorganic particle material was obtained. (Example 8) The same procedure as in Example 7 was performed except that 6 g of another wax (average particle size: 1.7 ⁇ m, surface potential: 4 mV) was used instead of the wax used in Example 7. An inorganic particle material was obtained.
  • (Comparative example 1) A commercially available silica particle material (manufactured by Admatex; SO-C2) was used as is.
  • (Comparative example 2) ⁇ Synthesis of core-shell particles> 6 g of acrylic resin (average particle size 300 nm, surface potential +52 mV) was mixed with 1000 g of a mother liquor consisting of 10% by mass of ABA type block copolymer (HLB 7.9, average molecular weight 2900), 30% by mass of ethanol, and the balance water. (Core material dispersion preparation process). Subsequently, 30 g of tetraethyl orthosilicate was stirred and mixed (complex formation step). Thereafter, the same operations as in Example 1 were performed to obtain fired silica.
  • ABA type block copolymer HLB 7.9, average molecular weight 2900
  • Comparative Silica 2 which is a test sample of this comparative example.
  • Comparative example 3 Calcined silica was obtained in the same manner as in Example 1, except that 6 g of wax (average particle size: 300 nm, surface potential -7 mV) was used instead of the acrylic resin used in Example 1.
  • the recovered silica was solidly aggregated and crushed in a mortar to obtain Comparative Silica 3, which is a test sample of this comparative example.
  • Comparative example 4 Comparative Silica 4, which is a test sample of this comparative example, was obtained by performing the same operation as in Example 1, except that a firing condition of 600° C. was used instead of the firing temperature of 1000° C. in Example 1.
  • Comparative example 5 Comparative Silica 5, which is a test sample of this comparative example, was obtained by performing the same operation as in Example 1, except that the concentration of the ABA type block copolymer in the mother liquor was 1% by mass.
  • Comparative example 6 Calcined silica was obtained in the same manner as in Example 1 except that 1000 g of water was used as the mother liquor. The recovered silica was solidly aggregated, and was crushed in a mortar to obtain comparative silica 6, which is a test sample of this comparative example.
  • Example 7 The same operation as in Example 1 was carried out, except that the mother liquor was prepared using another ABA type block copolymer (HLB 9.3, average molecular weight 4200) instead of the ABA type block copolymer used in Example 1. Comparative Silica 7, which is a test sample of this comparative example, was obtained.
  • Comparative example 8 The same operation as in Example 1 was carried out, except that the mother liquor was prepared using another ABA type block copolymer (HLB 2.5, average molecular weight 2000) instead of the ABA type block copolymer used in Example 1. Comparative Silica 8, which is a test sample of this comparative example, was obtained.
  • Comparative example 9 The same operation as in Example 1 was carried out, except that the mother liquor was prepared using another ABA type block copolymer (HLB 15.7, average molecular weight 8350) instead of the ABA type block copolymer used in Example 1. Comparative Silica 9, which is a test sample of this comparative example, was obtained.
  • the appearance of the silica obtained in Example 1 is shown in FIG. 1.
  • the silica obtained in Example 1 has a shell (shell layer) thickness of about 20 nm and a hollow particle size of about 220 nm and about 110 nm. It is clear that it is an inorganic particulate material.
  • the reason for the mixture of two particle sizes is that the core material used for template synthesis consists of two types of particle sizes.
  • a homogeneous slurry composition was obtained by suspending this hollow inorganic particle material in isopropyl alcohol and subjecting it to French press treatment (extrusion pressure 120 MPa).
  • FIG. 2(a) shows the particle size distribution obtained using a laser diffraction particle size distribution measuring device.
  • the true specific gravity of the shell layer ( ⁇ He ) was smaller than 2.39 g/cm 3 , and it was concluded that a substantially pore-free shell layer was formed.
  • the hollowness ratio was calculated to be 37%.
  • This hollow inorganic particle material has a region inside the particle that is separated from the outside by a shell layer through which molecules such as solvents and resins cannot pass. Since the interior of the particle is not surface-treated, the silanol groups present on the interior surface remain intact even if a sufficient amount of surface treatment agent is used. Such unreacted silanol groups can be identified.
  • Example 1 The test samples of Example 1 and Comparative Example 1 were subjected to elemental analysis by ICP emission spectrometry (Table 2) and ion analysis of the extracted water (Table 3).
  • Table 2 the silica was of high purity, containing almost no elements other than silica, and the extracted water contained almost no ions that would cause problems in semiconductor applications.
  • Comparative Example 1 is solid silica synthesized by the deflagration method (Patent Document 11), which is commonly used in the field targeted by the present technology. In comparison with this example, it did not contain any particularly problematic elements, and the amount of impurities at one minute was significantly lower than that of the comparative example.
  • FIG. 4 shows an observed cross section of the cut resin piece. Particles buried inside appeared as white spheres, and those present in the cross section showed dark depressions within the white outline. No resin is infiltrated inside the hollow inorganic particles.
  • the hollow inorganic particle material of Example 1 and the solid silica of Comparative Example 1 were mixed at a mass ratio of 1:2 (under conditions of approximately the same volume) and 1:1.
  • a resin composition was created using this mixed powder, and the relative dielectric constant and coefficient of thermal expansion of the resin piece were determined (Figure 5).
  • the relative permittivity decreased as the proportion of hollow inorganic particles increased.
  • the coefficient of thermal expansion showed approximately constant values for both CTE1 and CTE2. Therefore, it can be said that hollow inorganic particles are suitable for use in improving dielectric properties while maintaining thermomechanical properties.
  • Example 2 to 8 hollow inorganic particles were obtained similarly to Example 1.
  • Comparative Examples 2 to 9 the particles became pumice-like aggregates and were not independent particles, a sufficiently strong shell layer could not be formed, or the shell layer was not sufficiently densified, resulting in meso-fine particles penetrating into the lumen.
  • the obtained particles had pores and could not be called hollow inorganic particles.
  • Table 1 shows the classification of the particles obtained for these Examples and Comparative Examples, and the analysis results of average particle diameter, specific surface area, true specific gravity, and hollow ratio for particles obtained.
  • Table 4 also shows the relative dielectric constant and dielectric loss tangent values for the test sample of Example 1 whose surface was treated with HMDS and phenylaminosilane, and the test samples of Example 4 and Example 7 whose surface was treated with HMDS. I mentioned it.
  • Comparative Example 2 is an example in which the Stober method is applied mutatis mutandis, and its appearance is shown in FIG. Although a shell layer appeared to be formed, it was an aggregate of primary particles that were strongly bonded to each other and could not be broken up. In Example 1, such sintering was not observed.
  • the key point of this technology is to use a microphase-separated structure using a surfactant to attach a sufficiently thick shell layer when forming core/shell particles.
  • the Stober method when the Stober method was applied, the hydrolyzate of the hydrolyzable silane could not be uniformly attached to the hydrophilic part of the L3 phase lamella that was created, and the result was that it was locally accumulated. Conceivable. That is, it is considered that hydrolysis progressed before the reaction solution became homogeneous.
  • Comparative Example 3 is a synthesis example using a core material whose surface potential is -7 mV, and its appearance is shown in FIG. 7. As this shows, the product is a waffle-shaped sintered body.
  • Non-Patent Document 3 describes nanostructure control of fine particles in spray pyrolysis, and explains that porous silica is produced from a core material and a silica nucleus that have the same (negative in this case) surface potential.
  • the present technique does not involve a spraying step, it is clear that a homogeneous system also produces a precursor that provides a porous structure. Therefore, it can be said that the surface potential of the core material needs to be sufficiently different from that of silica, preferably positively charged.
  • Example 8 inorganic hollow particles were obtained in a synthesis example using a core material whose surface potential was +4 mV. From this, it is inferred that the surface potential of the core material, which determines whether or not the desired inorganic hollow particles can be obtained, is around -3 mV, which is between Comparative Example 3 and Example 8.
  • Comparative Example 4 is a comparative example for determining firing conditions, and the true specific gravity was the same as that of silica. Although these particles are apparently the same as the inorganic hollow particles of Example 1, it is thought that the shell layer is incompletely densified and mesopores remain.
  • the effects of the concentration of surfactant added can be compared in Examples 1 to 3 and Comparative Examples 5 to 6.
  • the concentrations of surfactants in these mother liquors are, in order, 10% by weight, 5% by weight, 2% by weight, 1% by weight, and 0% by weight.
  • a comparison of the appearance of silica produced under each condition is shown in FIG.
  • the surfactant concentration was about 1% by mass, a large amount of amorphous silica was mixed. In other words, under dilute conditions, the remaining hydrolyzate that could not be adsorbed to the hydrophilic part of the surfactant accumulated and polymerized on its own.
  • Example 4 and Comparative Examples 7 to 9 are examples to show the effects of changing the molecular weight of the Pluronic surfactant and the size of the hydrophobic block.
  • Example 4 and Comparative Example 7 materials with almost the same HLB as Example 1 were used to examine the effect of molecular weight.
  • the specific surface area of the inorganic hollow particles of Example 4 was smaller than that of Examples.
  • Comparative Example 7 had a very large specific surface area. This can be explained as follows.
  • the silica core of this embodiment has a microphase-separated structure containing silicic acid oligomers between lamellar layers created by adsorption of a hydrolyzate of a hydrolyzable silane to a polar block of a surfactant, and is locally mesoporous. It can be considered silica.
  • the surfactant is removed by calcination, leaving mesopores.
  • Example 5 is an example using a BAB type block copolymer
  • Example 6 is an example using an AB type block copolymer.
  • Hollow inorganic particles similar to those in Example 1 were obtained using either surfactant. In this way, the block structure of the surfactant is not a problem, and the desired hollow structure can be obtained by appropriately selecting the HLB of the surfactant.
  • Examples 7 and 8 can be compared in terms of the effects obtained by changing the size and material of the core material.
  • this technology by changing the size of the core material, it is possible to change the particle size of the inorganic hollow particles.
  • by changing the quantitative ratio of hydrolyzable silane and core material it is possible to produce inorganic hollow particles with different hollow ratios.
  • FIG. (a) and (b) are observations of the surface and inner surface of hollow inorganic particles, respectively, and in both cases it can be seen that a spongy random structure derived from the L3 phase remains.
  • (c) is a particle cross-section observed using a resin flake containing hollow inorganic particles, and traces of a spongy random structure derived from the L3 phase can be seen as a striped pattern on the end face (top left).
  • Silica according to the present technology can be suitably used as a filler added to semiconductor materials in terms of purity and dielectric properties.

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Abstract

La présente invention aborde le problème de la fourniture d'une méthode de production d'un matériau particulaire inorganique creux qui a une constante diélectrique relative suffisamment faible et une tangente de perte diélectrique suffisamment faible, et contient une petite quantité d'impuretés ioniques. Une méthode de production d'un matériau particulaire inorganique creux selon la présente invention comprend : une étape de préparation de liquide de dispersion de matériau de noyau dans laquelle un liquide de dispersion de matériau de noyau est préparé par dispersion d'un matériau de noyau dans un liquide de base qui est un mélange d'un tensioactif non ionique et d'un milieu de dispersion qui contient de l'eau et contient éventuellement un solvant aqueux ; une étape de formation de corps composite dans laquelle un produit d'hydrolyse d'un silane hydrolysable est mélangé et agité dans le liquide de dispersion de matériau de noyau, formant ainsi un corps composite d'adsorption, le produit d'hydrolyse étant adsorbé sur la surface du matériau de noyau ; une étape de formation de corps composite noyau-enveloppe dans laquelle un corps composite noyau-enveloppe est obtenu par réalisation d'une réaction de polymérisation par condensation du produit d'hydrolyse du corps composite d'adsorption dans le liquide de base ; et une étape de cuisson dans laquelle le matériau de noyau est retiré par cuisson du corps composite noyau-enveloppe.
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Citations (3)

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JP2021054685A (ja) * 2019-09-30 2021-04-08 日揮触媒化成株式会社 シリカを含む外殻の内側に空洞を有する粒子とその製造方法、該粒子を含む塗布液、及び該粒子を含む透明被膜付基材
WO2021172294A1 (fr) * 2020-02-27 2021-09-02 Ａｇｃ株式会社 Particules creuses de silice et son procédé de production
JP2022026614A (ja) * 2020-07-31 2022-02-10 日東電工株式会社 プリント基板用樹脂組成物及び樹脂成形体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021054685A (ja) * 2019-09-30 2021-04-08 日揮触媒化成株式会社 シリカを含む外殻の内側に空洞を有する粒子とその製造方法、該粒子を含む塗布液、及び該粒子を含む透明被膜付基材
WO2021172294A1 (fr) * 2020-02-27 2021-09-02 Ａｇｃ株式会社 Particules creuses de silice et son procédé de production
JP2022026614A (ja) * 2020-07-31 2022-02-10 日東電工株式会社 プリント基板用樹脂組成物及び樹脂成形体

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