WO2023100676A1 - 中空シリカ粒子及びその製造方法 - Google Patents

中空シリカ粒子及びその製造方法 Download PDF

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WO2023100676A1
WO2023100676A1 PCT/JP2022/042755 JP2022042755W WO2023100676A1 WO 2023100676 A1 WO2023100676 A1 WO 2023100676A1 JP 2022042755 W JP2022042755 W JP 2022042755W WO 2023100676 A1 WO2023100676 A1 WO 2023100676A1
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Prior art keywords
hollow silica
silica particles
particles
density
oil
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PCT/JP2022/042755
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English (en)
French (fr)
Japanese (ja)
Inventor
博道 加茂
肇 片山
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AGC Si Tech Co Ltd
AGC Inc
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Asahi Glass Co Ltd
AGC Si Tech Co Ltd
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Priority to JP2023564875A priority Critical patent/JPWO2023100676A1/ja
Priority to KR1020247017704A priority patent/KR20240112850A/ko
Priority to CN202280079036.6A priority patent/CN118317921A/zh
Publication of WO2023100676A1 publication Critical patent/WO2023100676A1/ja
Priority to US18/675,502 priority patent/US20240308858A1/en
Anticipated expiration legal-status Critical
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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
    • 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
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Definitions

  • the present invention relates to hollow silica particles and a method for producing the same.
  • Patent Document 1 describes a resin composition containing (A) an epoxy resin, (B) a curing agent, (C) hollow silica, and (D) fused silica.
  • Patent Document 2 in a low dielectric resin composition containing hollow particles and a thermosetting resin, as hollow particles, 98% by mass or more of the entire shell is formed of silica, and the average porosity is 30 to 30%.
  • a low dielectric resin composition having a content of 80% by volume and an average particle size of 0.1 to 20 ⁇ m is described.
  • hollow silica particles when conventional hollow silica particles are added to a solvent, the solvent penetrates into the inside of the particles, making it impossible to use them for their intended purpose.
  • the inside of the particles is impregnated with methyl ethyl ketone, the viscosity of the composition increases, and the amount of hollow silica particles added cannot be increased, achieving a sufficiently low relative dielectric constant. could not.
  • the hollow silica material described in Patent Document 3 in its example, coats the inorganic compound of the template with silica, removes the template, and then adds silica sol for aging to obtain hollow silica particles.
  • the inorganic compound of the template tends to aggregate, and there are problems such as aggregation between primary particles and an inability to control the size of aggregates.
  • the point where the primary particles are agglomerated tends to be a defect of the shell of the hollow silica, and the resin varnish is entrapped there, so that the dispersibility tends to deteriorate.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide new hollow silica particles that have sufficiently small relative permittivity and dielectric loss tangent and are excellent in dispersibility in resin. do.
  • the present invention relates to the following (1) to (18).
  • the hollow silica particles according to (1) or (2) above which have a density of 2.00 to 2.35 g/cm 3 as determined by density measurement with a dry pycnometer using helium gas.
  • the hollow silica particles according to any one of (1) to (3) having an average primary particle size of 50 nm to 10 ⁇ m.
  • the total concentration of one or more metals M selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba contained in the hollow silica particles is 50 ppm by mass or more.
  • (11) The hollow silica particles according to any one of (1) to (10), wherein the kneaded product containing the hollow silica particles has a viscosity of 10000 mPa ⁇ s or less as measured by the following measuring method.
  • the density of the particles obtained by density measurement with a dry pycnometer using argon gas is A (g/cm 3 ), and 6 parts by mass of boiled linseed oil and the hollow silica particles (6 ⁇ A/2.2) are The kneaded product obtained by mixing and kneading at 2000 rpm for 3 minutes is measured with a rotary rheometer at a shear rate of 1 s ⁇ 1 for 30 seconds to determine the viscosity at 30 seconds.
  • the molar ratio (Q3/Q4) of the Q3 structure having one silanol-derived OH group to the Q4 structure having no silanol-derived OH group, measured by solid 29 Si-DD/MAS-NMR, is The hollow silica particles according to any one of (1) to (11) above, which are 2 to 40%.
  • the hollow silica particles of the present invention have a dense shell layer and a small specific surface area, so both the dielectric constant and the dielectric loss tangent can be made sufficiently small. Solvents such as methyl ethyl ketone and N-methylpyrrolidone hardly permeate the hollow silica particles of the present invention, so they can exhibit excellent low dielectric constant and low dielectric loss tangent even in resin compositions. Moreover, the hollow silica particles of the present invention have an appropriate specific surface area and are excellent in dispersibility in resins.
  • FIG. 1 shows a scanning electron microscope image (SEM image) of the hollow silica particles obtained in Example 1.
  • FIG. 1 shows a scanning electron microscope image (SEM image) of the hollow silica particles obtained in Example 1.
  • the hollow silica particles of the present invention have a shell layer (solid film) containing silica, and have a space inside the shell layer. It can be confirmed by transmission electron microscope (TEM) observation or scanning electron microscope (SEM) observation that the hollow silica particles have a space inside the shell layer. In the case of SEM observation, it can be confirmed that the particles are hollow by observing partially opened broken particles. Spherical particles having internal spaces that can be confirmed by TEM observation or SEM observation are defined as “primary particles”. In the hollow silica particles, the primary particles are partially bonded to each other by the firing and drying processes, so the hollow silica particles obtained in the production are often aggregates of secondary particles in which the primary particles are aggregated. .
  • the shell layer "containing silica” means that silica (SiO 2 ) is contained in an amount of 50% by mass or more.
  • the composition of the shell layer can be measured by ICP emission spectrometry, flame atomic absorption spectrometry, or the like.
  • Silica contained in the shell layer is preferably 80% by mass or more, more preferably 95% by mass or more. The upper limit is theoretically 100% by mass.
  • Silica contained in the shell layer is preferably less than 100% by mass, more preferably 99.99% by mass or less.
  • the residue includes alkali metal oxides and silicates, alkaline earth metal oxides and silicates, carbon and the like.
  • "having a space inside the shell layer” means a hollow state in which one space is surrounded by the shell layer when the cross section of one primary particle is observed. That is, one hollow particle has one large space and a shell layer surrounding it.
  • the hollow silica particles of the present invention have a structure in which the shell has a space, when the particles are added as a filler to a solvent, more space can be secured in the composition. Therefore, the dielectric constant can be lowered when used for an insulating layer of an electronic device or the like.
  • the hollow silica particles of the present invention have a particle density (hereinafter also referred to as Ar density) obtained by density measurement with a dry pycnometer using argon gas, A (g/cm 3 ), and a BET specific surface area of B (m 2 /g), the product (A ⁇ B) of the Ar density and the BET specific surface area is 1 to 120 m 2 /cm 3 .
  • a ⁇ B indicates the specific surface area per volume when the hollow silica particles are dispersed in a solvent. For example, when added to a resin, it indicates the specific surface area of the portion occupied by the hollow silica particles in a predetermined volume in the resin. .
  • the resin composition containing the hollow silica particles of the present invention is used for the insulating layer by satisfying the above relationship between the Ar density and the BET specific surface area of the particles, the dielectric constant of the insulating layer is lowered and the dielectric loss is reduced. Since it can be lowered, it is possible to provide a substrate that is sufficiently compatible with high-frequency circuits.
  • a ⁇ B is 120 m 2 /cm 3 or less, the specific surface area of silica in the solvent is so small that the viscosity of the composition does not increase excessively. If the viscosity of the composition is too high, the dielectric loss tangent may deteriorate.
  • a ⁇ B is preferably 80 m 2 /cm 3 or less, more preferably 40 m 2 /cm 3 or less, and even more preferably 20 m 2 /cm 3 or less. Also, it is practically difficult to fabricate a product with A ⁇ B smaller than the above.
  • a ⁇ B is preferably 2 m 2 /cm 3 or more, more preferably 2.5 m 2 /cm 3 or more, and even more preferably 3 m 2 /cm 3 or more.
  • the hollow silica particles of the present invention preferably have a particle density (Ar density) of 0.35 to 2.00 g/cm 3 as determined by density measurement with a dry pycnometer using argon gas.
  • Ar density 0.35 g/cm 3 or more, for example, the difference in specific gravity from the resin does not become too large, so the dispersibility in the resin composition can be improved.
  • Ar density 2.00 g/cm 3 or less, the effect of reducing the dielectric constant is likely to be exhibited.
  • the lower limit of Ar density is more preferably 0.40 g/cm 3 or more, and the upper limit is more preferably 1.50 g/cm 3 or less, further preferably 1.00 g/cm 3 or less.
  • the Ar density is more preferably 0.35 to 1.50 g/cm 3 and even more preferably 0.40 to 1.00 g/cm 3 .
  • the hollow silica particles of the present invention preferably have a density of 2.00 to 2.35 g/cm 3 as determined by density measurement with a dry pycnometer using helium gas (hereinafter also referred to as He density). . Since helium gas passes through minute voids, a density corresponding to the true density of the silica portion of the silica particles having a space inside can be obtained. When the He density is 2.00 g/cm 3 or more, the amount of residual silanol contained in the hollow silica particles is reduced, so the dielectric loss tangent is likely to be lowered.
  • the lower limit of He density is more preferably 2.05 g/cm 3 or more, more preferably 2.10 g/cm 3 or more, and the upper limit is more preferably 2.33 g/cm 3 or less. 0.30 g/cm 3 or less is more preferable.
  • the He density is more preferably 2.05 to 2.35 g/cm 3 and even more preferably 2.10 to 2.33 g/cm 3 .
  • the apparent density of hollow silica particles can also be measured using a pycnometer.
  • a sample (hollow silica particles) and an organic solvent are placed in a pycnometer, left to stand at 25° C. for 48 hours, and then measured. It may take time for the organic solvent to permeate depending on the density of the shell of the hollow silica particles.
  • the results measured by this method correspond to the results of density measurements by a dry pycnometer using argon gas.
  • the apparent density of the hollow silica particles of the present invention can be adjusted by adjusting the primary particle size and shell thickness. By changing the density of the particles, it is possible to control whether they settle in the solvent, remain dispersed, or float on top. When dispersing in a solvent, it is desirable that the density of the solvent and the apparent density of the particles are close to each other. For example, when it is desired to disperse the particles in water having a density of 1.0 g/cm 3 , it is preferable to adjust the apparent density of the particles to 0.8 g/cm 3 or more and 1.2 g/cm 3 or less.
  • the hollow particle ratio refers to the ratio of complete hollow particles having a hollow space inside without breaking the shell layer in the sample of hollow silica particles. Since the hollow silica particles of the present invention have a dense shell layer, various solvents, argon gas, and gases with a larger dynamic molecular diameter than argon molecules are difficult to permeate, but particles with a broken shell layer (broken particles) exists, it penetrates into it. Therefore, the apparent density changes with the hollow particle ratio. The higher the hollow particle ratio, the lower the apparent density of the hollow silica sample, and the lower the hollow particle ratio, the higher the apparent density of the hollow silica sample.
  • the hollow particle ratio can be obtained from the theoretical density obtained from the charged amount of raw materials and the apparent density measured with a dry pycnometer.
  • the hollow particle ratio can also be obtained from the change in weight during heat treatment using the cake after filtration before removing the oil core when producing the hollow silica particles.
  • the oil component in the broken particles volatilizes and the oil component in the complete hollow particles is retained.
  • the amount of change in weight during heat treatment when all of the charged oil components volatilize (hollow particle ratio 0%) and when all are retained (hollow particle ratio 100%) can be calculated from the charged amount of raw materials, so it is possible to calculate the weight change after filtration.
  • the hollow particle ratio is obtained from the change in weight when the overnight dried sample is heat-treated up to 800°C.
  • the hollow silica particles of the present invention preferably have a BET specific surface area of 1 to 100 m 2 /g. It is substantially difficult to make the BET specific surface area less than 1 m 2 /g. Further, when the BET specific surface area is 100 m 2 /g or less, the increase in viscosity of the resin composition can be suppressed, and the dispersibility in the resin composition does not deteriorate.
  • the BET specific surface area is preferably 1 to 100 m 2 /g, more preferably 1 to 50 m 2 /g, even more preferably 1 to 20 m 2 /g, most preferably 1 to 15 m 2 /g.
  • the BET specific surface area is measured using a specific surface area measuring device (for example, "Tristar II3020” manufactured by Shimadzu Corporation), and as a pretreatment, the hollow silica particles are dried at 230 ° C. to 50 mTorr, It can be measured by a multi-point method using nitrogen gas.
  • a specific surface area measuring device for example, "Tristar II3020” manufactured by Shimadzu Corporation
  • the sphericity of the hollow silica particles is preferably 0.75 to 1.0. When the sphericity is low, the hollow silica particles are likely to be broken, the Ar density is lowered, the specific surface area is increased, and the dielectric loss tangent may be increased.
  • the sphericity is the maximum diameter (DL) and the minimum diameter (DS) perpendicular to each of the 100 arbitrary particles in a photographic projection obtained by photographing with a scanning electron microscope (SEM). is measured, and the ratio of the minimum diameter (DS) to the maximum diameter (DL) (DS/DL) is calculated and can be expressed as an average value.
  • the sphericity is more preferably 0.80 or more, more preferably 0.82 or more, even more preferably 0.83 or more, particularly preferably 0.85 or more, and 0.85 or more. 87 or higher is particularly preferred, and 0.90 or higher is most preferred.
  • the size of the primary particles of the hollow silica particles is obtained by directly observing the particle size (diameter) by SEM observation. Specifically, the size of the primary particles of 100 particles is measured from the SEM image, and the distribution of the size of the primary particles (particle size) obtained by aggregating them is compared with the size of the overall primary particles. is estimated to be the distribution of By SEM observation, it is possible to directly measure the primary particle size of particles that are difficult to deagglomerate. Since the size of the primary particles is reflected in the particle surface state of the aggregated particles, it becomes a parameter that determines the specific surface area and oil absorption.
  • the average size of the primary particles is preferably in the range of 50 nm to 10 ⁇ m.
  • the average primary particle diameter is less than 50 nm, the specific surface area, oil absorption and pore volume increase, the amount of SiOH on the particle surface and the amount of adsorbed water increase, and the dielectric loss tangent tends to increase.
  • the average primary particle size is 10 ⁇ m or less, it is easy to handle as a filler.
  • the lower limit of the average primary particle size is more preferably 70 nm or more, most preferably 100 nm or more, and the upper limit is more preferably 5 ⁇ m or less, particularly preferably 3 ⁇ m or less.
  • the hollow silica particles of the present invention preferably have the above average primary particle size, and among the primary particles, 35% or more of the whole particles preferably have a particle size within ⁇ 40% of the average primary particle size.
  • the particle size of 35% or more of the particles is within ⁇ 40% of the average primary particle size, the size of the hollow silica particles becomes uniform, and shell defects of the hollow silica particles are less likely to occur.
  • 40% or more of the total particles have an average primary particle size within ⁇ 40%, more preferably 50% or more of the total particles have an average primary particle size within ⁇ 40%, and 60% or more of the total particles. is particularly preferably within ⁇ 40% of the average primary particle diameter, and most preferably 70% or more of all the particles are within ⁇ 40% of the average primary particle diameter.
  • the median diameter (D50) of the secondary particles of the hollow silica particles is preferably 0.1 to 10 ⁇ m.
  • the median diameter (D50) is more preferably 0.2 ⁇ m or more, still more preferably 0.25 ⁇ m or more, and particularly preferably 0.3 ⁇ m or more.
  • the median diameter is too large, it may cause graininess when the resin composition is molded into a film.
  • 3 ⁇ m or less is most preferable.
  • the coarse particle size (D90) of the secondary particles of the hollow silica particles is preferably 1 to 30 ⁇ m.
  • the coarse particle size is preferably 1 ⁇ m or more.
  • the coarse particle size is preferably 30 ⁇ m or less.
  • the lower limit of the coarse particle size is more preferably 3 ⁇ m or more, most preferably 5 ⁇ m or more, and the upper limit is preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, further preferably 20 ⁇ m or less, and most preferably 15 ⁇ m or less. .
  • the coarse particle size is also obtained by measuring the particle size of the secondary particles by laser scattering.
  • the shell thickness of the hollow silica particles is preferably 0.01 to 0.3 with respect to 1 of the diameter of the primary particles. When the shell thickness is less than 0.01 to 1 of the diameter of the primary particles, the strength of the hollow silica particles may decrease. If this ratio is larger than 0.3, the internal space becomes small, and the characteristics of the hollow shape are lost.
  • the shell thickness is more preferably 0.02 or more, more preferably 0.03 or more, more preferably 0.2 or less, and 0.1 or less with respect to the diameter 1 of the primary particle. More preferred.
  • the shell thickness is obtained by measuring the shell thickness of individual particles with a transmission electron microscope (TEM).
  • hollow silica particles have a space inside, they can enclose substances inside the particles. Since the hollow silica particles of the present invention have a dense shell layer, it is difficult for various solvents to permeate them. Therefore, the oil absorption varies with the proportion of broken particles.
  • the oil absorption of the hollow silica particles is preferably 15-1300 mL/100 g.
  • the oil absorption is 15 mL/100 g or more, adhesion to the resin can be ensured when used in the resin composition, and when it is 1300 mL/100 g or less, the strength of the resin can be secured when used in the resin composition. It can reduce the viscosity of the material. If the oil absorption is large, the viscosity of the resin composition increases, so the oil absorption of the hollow silica particles is more preferably 1000 mL/100 g or less, more preferably 700 mL/100 g or less.
  • 500 mL/100 g or less is particularly preferred, and 200 mL/100 g or less is most preferred. Also, if the oil absorption is too low, the adhesion between the powder and the resin may deteriorate, so it is more preferably 20 mL/100 g or more.
  • the oil absorption can be measured according to JIS K5101-13-2:2004, and it is preferable to use boiled linseed oil.
  • the oil absorption can be adjusted by adjusting the ratio of the broken particles based on the relationship between the ratio of the broken particles and the oil absorption as described above. Furthermore, since the space between the primary particles is also a space that can hold oil, the larger the median diameter of the secondary particles, which are aggregates of the primary particles, the greater the oil absorption, and the smaller the median diameter of the secondary particles, the greater the oil absorption. It is possible that there will be less.
  • the hollow silica particles preferably contain one or more metals M selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba.
  • metals M selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba.
  • the metal M is contained between the reaction process and the washing process in the production of hollow silica particles.
  • Metal M can be contained in the hollow silica particles by washing.
  • the concentration of metal M contained in the hollow silica particles is preferably 50 ppm by mass or more and 1% by mass or less.
  • the concentration of the metals M is 50 mass ppm or more, the condensation of the bound silanol groups is promoted due to the flux effect during firing, and the remaining silanol groups can be reduced, thereby reducing the dielectric loss tangent. If the concentration of the metal M is too high, the amount of components that react with silica to form silicates increases, and the hygroscopicity of the hollow silica particles may deteriorate.
  • the concentration of the metal M is more preferably 100 ppm by mass or more, more preferably 150 ppm by mass or more, preferably 1% by mass or less, more preferably 5000 mass ppm or less, and most preferably 1000 mass ppm or less.
  • the metal M can be measured by ICP emission spectrometry after adding perchloric acid and hydrofluoric acid to the hollow silica particles and igniting them to remove silicon as the main component. Further, when an alkali metal silicate is used as the silica raw material, the carbon (C) component derived from the raw material is less in the shell layer of the obtained hollow silica particles than when silicon alkoxide is used as the silica raw material.
  • the hollow silica particles of the present invention preferably have a viscosity of 10,000 mPa ⁇ s or less when a kneaded material containing the hollow silica particles is measured by the following measuring method.
  • Measurement method 6 parts by mass of boiled linseed oil and hollow silica particles (6 ⁇ A/2.2) by mass were mixed, with the density of the particles determined by density measurement with a dry pycnometer using argon gas as A (g/cm 3 ). Then, the kneaded product obtained by kneading at 2000 rpm for 3 minutes is measured with a rotary rheometer at a shear rate of 1 s ⁇ 1 for 30 seconds to determine the viscosity at 30 seconds.
  • the kneaded product has a viscosity of 10000 mPa s or less at a shear rate of 1 s ⁇ 1 obtained by the above measurement method, the amount of solvent added during molding and film formation of the resin composition containing hollow silica particles can be reduced, and the drying speed can be increased. You can do it faster and improve your productivity.
  • the viscosity tends to increase when added to the resin composition. is small, an increase in the viscosity of the resin composition can be suppressed.
  • the viscosity of the kneaded product is more preferably 8000 mPa ⁇ s or less, still more preferably 5000 mPa ⁇ s or less, and most preferably 4000 mPa ⁇ s or less.
  • the lower the viscosity of the kneaded product at a shear rate of 1 s ⁇ 1 the better the coating properties of the resin composition and the higher the productivity, so the lower limit is not particularly limited.
  • Silica particles are classified into four types of basic structures represented by Q1 to Q4 according to the degree of linkage of SiO 4 tetrahedra in 29 Si-NMR spectrum assignment.
  • Q1 to Q4 are as follows.
  • Q1 is a structural unit having one Si around Si through oxygen, and a SiO 4 tetrahedron is connected to another SiO 4 tetrahedron, and a solid 29 Si-DD/MAS-NMR It has a peak around -80 ppm in the spectrum.
  • Q2 is a structural unit having two Si around Si via oxygen, and a SiO 4 tetrahedron is linked to two other SiO 4 tetrahedra, and a solid 29 Si-DD/MAS-NMR It has a peak around ⁇ 91 ppm in the spectrum.
  • Q3 is a structural unit having three Si around Si via oxygen, and a SiO 4 tetrahedron is linked to three other SiO 4 tetrahedra, and a solid 29 Si-DD/MAS-NMR It has a peak around ⁇ 101 ppm in the spectrum.
  • Q4 is a structural unit having four Si around Si via oxygen, and the SiO 4 tetrahedron is connected to four other SiO 4 tetrahedra, and solid 29 Si-DD/MAS-NMR It has a peak around -110 ppm in the spectrum.
  • the hollow silica particles of the present invention have a molar ratio of a Q3 structure having one silanol-derived OH group to a Q4 structure having no silanol-derived OH group (Q3 /Q4) is preferably 2 to 40%.
  • Q3/Q4 is 40% or less, the amount of silanol can be suppressed and the dielectric loss tangent is improved. It is practically difficult to obtain a material having a Q3/Q4 ratio of less than 2% because it requires firing at a high temperature, and the hollow portion of the hollow silica shrinks during this process.
  • Q3/Q4 is more preferably 30% or less, and even more preferably 20% or less.
  • Q3/Q4 of hollow silica particles is measured as follows.
  • a hollow silica particle powder is used as a measurement sample.
  • a nuclear magnetic resonance apparatus of 400 MHz is used, a CP/MAS probe with a diameter of 7.5 mm is mounted, 29 Si is used as the observed nuclei, and measurements are performed by the DD/MAS method.
  • the measurement conditions were as follows: 29 Si resonance frequency of 79.43 MHz, 29 Si 90° pulse width of 5 ⁇ s, 1H resonance frequency of 399.84 MHz, 1H decoupling frequency of 50 kHz, MAS rotation speed of 4 kHz, spectrum width of 30.49 kHz,
  • the measurement temperature shall be 23°C.
  • each peak of the spectrum after the Fourier transform is optimized using the nonlinear least-squares method with the variable parameters of the center position, height, and half width of the peak shape created by mixing Lorentzian and Gaussian waveforms. .
  • Targeting the four structural units of Q1, Q2, Q3 and Q4, the molar ratio of Q3 and Q4 is calculated from the obtained Q1 content, Q2 content, Q3 content and Q4 content.
  • the content of silanol groups in silica particles is measured by the DD/MAS method (Dipolar Decoupling/Magic Angle Spinning), not by the CP/MAS method (Cross Polarization/Magic Angle Spinning).
  • the CP/MAS method 1 H sensitizes and detects Si present in the vicinity, so the peaks obtained accurately indicate the content of Q1, Q2, Q3, and Q4. not reflected in
  • the DD/MAS method does not have the sensitizing effect of the CP/MAS method, so the peaks obtained accurately reflect the Q1 content, Q2 content, Q3 content, and Q4 content. , suitable for quantitative analysis.
  • the pore volume of the hollow silica particles is preferably 0.2 cm 3 /g or less. If the pore volume is more than 0.2 cm 3 /g, it tends to absorb moisture, and the dielectric loss of the resin composition may deteriorate.
  • the pore volume is more preferably 0.15 cm 3 /g or less, still more preferably 0.1 cm 3 /g or less, and particularly preferably 0.05 cm 3 /g or less.
  • the pore volume is determined by the BJH method based on the nitrogen adsorption method using a specific surface area/pore distribution measuring device (e.g., "BELSORP-miniII” manufactured by Microtrac Bell, “Tristar II” manufactured by Micromeritic, etc.). Calculated by
  • the surfaces of the hollow silica particles are preferably treated with a silane coupling agent.
  • a silane coupling agent By treating the surface of the hollow silica particles with a silane coupling agent, the amount of residual surface silanol groups is reduced, the surface is made hydrophobic, moisture adsorption can be suppressed, dielectric loss can be improved, and the resin composition and At this time, the affinity with the resin is improved, and the dispersibility and the strength after forming the resin film are improved.
  • silane coupling agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, and organosilazane compounds.
  • Silane coupling agents may be used alone or in combination of two or more.
  • the amount of the silane coupling agent attached is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and even more preferably 2 parts by mass or more with respect to 100 parts by mass of the hollow silica particles. Moreover, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less. That is, the amount of the silane coupling agent attached is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the hollow silica particles.
  • the fact that the surface of the hollow silica particles is treated with the silane coupling agent can be confirmed by detecting the peak due to the substituent of the silane coupling agent by IR. Moreover, the adhesion amount of the silane coupling agent can be measured by the amount of carbon.
  • the hollow silica particles of the present invention preferably have a dielectric constant of 1.3 to 5.0 at 1 GHz. Especially in the measurement of the dielectric constant of powder, the sample space becomes small and the measurement accuracy deteriorates at 10 GHz or more, so the measurement value at 1 GHz is adopted in the present invention.
  • the dielectric constant at 1 GHz is within the above range, a low dielectric constant required for electronic devices can be achieved.
  • the lower limit of the dielectric constant at 1 GHz is preferably 1.3 or more, more preferably 1.4 or more.
  • the upper limit is more preferably 4.5 or less, more preferably 4.0 or less, particularly preferably 3.5 or less, even more preferably 3.0 or less, and most preferably 2.5 or less.
  • the hollow silica particles of the present invention preferably have a dielectric loss tangent at 1 GHz of 0.0001 to 0.05.
  • the dielectric loss tangent at 1 GHz is 0.05 or less, the low dielectric constant required for electronic devices can be achieved.
  • the lower limit of the dielectric loss tangent at 1 GHz is more preferably 0.0002 or more, more preferably 0.0003 or more.
  • the upper limit is more preferably 0.01 or less, more preferably 0.005 or less, even more preferably 0.003 or less, particularly preferably 0.002 or less, particularly preferably 0.0015 or less, and 0.01 or less. 0010 or less is most preferred.
  • the dielectric constant and dielectric loss tangent can be measured by the perturbation resonator method using a dedicated device (eg, "Vector Network Analyzer E5063A” manufactured by Keycom Co., Ltd.).
  • a dedicated device eg, "Vector Network Analyzer E5063A” manufactured by Keycom Co., Ltd.
  • the hollow silica particles of the present invention can be mixed with a resin and used as a resin composition.
  • the resin composition according to this embodiment contains the hollow silica particles of the present invention and a resin.
  • the content of hollow silica particles in the resin composition is preferably 5 to 70% by mass, more preferably 10 to 50% by mass.
  • polyesters such as polybutylene terephthalate, polyethylene terephthalate, unsaturated polyesters and aromatic polyesters
  • fluororesin such as fluoropropylene copolymer (FEP), tetrafluoroethylene-ethylene copolymer (ETFE); epoxy resin; silicone resin; phenolic resin; melamine resin; urea resin; polyimide; polyphenylene ether; polyphenylene sulfide; polysulfone; liquid crystal polymer; polyether sulfone; polycarbonate; maleimide-modified resin; ABS (acrylonitrile-butadiene-styrene) resin; ⁇ One or two or more selected from diene rubber-styrene resins and the like can be used. Since the dielectric loss tangent in the resin composition also depends on the properties of the resin, the resin to be used should be selected in consideration of these properties.
  • the hollow silica particles of the present invention can be used as a filler for slurry compositions.
  • the slurry composition refers to a muddy composition in which the hollow silica particles of the present invention are dispersed in an aqueous or oil medium.
  • the slurry composition preferably contains 1 to 40% by mass of hollow silica particles, more preferably 5 to 40% by mass.
  • Oil-based media include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene,
  • Examples include methyl ethyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methylpyrrolidone, n-hexane, cyclohexane, cyclohexanone and naphtha which is a mixture thereof. These may be used alone or as a mixture of two or more.
  • the resin composition and slurry composition may contain optional components in addition to the above resin and medium.
  • optional components include dispersing aids, surfactants, fillers other than silica, and the like.
  • the dielectric constant thereof is preferably 2.0 to 3.5 at a frequency of 10 GHz, and the lower limit is 2.0.
  • the upper limit is more preferably 2 or more, more preferably 2.3 or more, and the upper limit is more preferably 3.2 or less, further preferably 3.0 or less.
  • the relative permittivity of the resin film at a frequency of 10 GHz is within the above range, it is expected to be used in electronic devices, communication devices, etc., because it has excellent electrical properties.
  • the dielectric loss tangent of the resin film is preferably 0.01 or less, more preferably 0.008 or less, and even more preferably 0.0065 or less at a frequency of 10 GHz.
  • the resin film has excellent electrical properties, and is expected to be used in electronic devices, communication devices, and the like. Since the transmission loss of the circuit is suppressed as the dielectric loss tangent becomes smaller, the lower limit value is not particularly limited.
  • the dielectric constant and dielectric loss tangent of the resin film can be measured using a split post dielectric resonator (SPDR) (manufactured by Agilent Technologies, for example).
  • SPDR split post dielectric resonator
  • the resin film preferably has an average coefficient of linear expansion of 10 to 50 ppm/°C.
  • the average coefficient of linear expansion is within the above range, the range is close to the coefficient of thermal expansion of copper foil, which is widely used as a base material, and thus the electrical properties are excellent.
  • the average coefficient of linear expansion is more preferably 12 ppm/°C or higher, more preferably 15 ppm/°C or higher, and more preferably 40 ppm/°C or lower, further preferably 30 ppm/°C or lower.
  • the average coefficient of linear expansion is measured by using a thermomechanical analyzer (for example, "TMA-60” manufactured by Shimadzu Corporation), heating the resin film at a load of 5 N and a temperature increase rate of 2 ° C./min, and increasing from 30 ° C. It is obtained by measuring the dimensional change of the sample up to 150° C. and calculating the average.
  • a thermomechanical analyzer for example, "TMA-60” manufactured by Shimadzu Corporation
  • the peel strength when the resin film is laminated with metal is 30 N/mm or more.
  • the peel strength is preferably 30 N/mm or more, more preferably 40 N/mm or more, and most preferably 50 N/mm or more.
  • the peel strength can be measured using a 90° peel tester or the like after laminating the resin composition on the metal.
  • an oil-in-water emulsion containing an aqueous phase, an oil phase, and a surfactant is used to obtain a hollow silica precursor in the emulsion, and the hollow silica is obtained from the precursor.
  • Methods of obtaining particles are included.
  • This oil-in-water emulsion is an emulsion in which an oil phase is dispersed in water.
  • an oil-in-water emulsion containing an aqueous phase, an oil phase and a surfactant is prepared, and the oil-in-water emulsion is allowed to stand for 0.5 to 240 hours to obtain an oil-in-water emulsion.
  • the first silica raw material is added to the oil-in-water emulsion to form the first-stage shell
  • the second silica raw material is added to the emulsion in which the first-stage shell is formed.
  • an oil-in-water emulsion is also simply referred to as an emulsion.
  • the dispersion liquid in which the oil core-silica shell particles are dispersed is produced by adding the first silica raw material and before the second silica raw material is added, and the oil core after the addition of the second silica raw material -
  • a dispersion in which silica shell particles are dispersed may also be referred to as an emulsion.
  • the dispersion in which the oil core-silica shell particles are dispersed after the latter second silica raw material is added may be equivalent to the hollow silica precursor dispersion.
  • a first silica raw material is added to an oil-in-water emulsion containing an aqueous phase, an oil phase, and a surfactant to form a first-stage shell.
  • the aqueous phase of the emulsion mainly contains water as a solvent. Additives such as water-soluble organic liquids and water-soluble resins may be further added to the aqueous phase.
  • the proportion of water in the aqueous phase is preferably 50-100% by mass, more preferably 90-100% by mass.
  • the oil phase of the emulsion preferably contains a water-insoluble organic liquid that is incompatible with the aqueous phase components. This organic liquid droplets in the emulsion and forms the oil-core portion of the hollow silica precursor.
  • organic liquids examples include n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-pentane, isopentane, n-decane, isodecane, n-dodecane, isododecane, and pentadecane.
  • paraffinic base oils such as paraffinic base oils, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclohexene, or mixtures thereof such as naphthenic base oils, benzene, toluene, xylene , ethylbenzene, propylbenzene, cumene, mesitylene, tetralin, styrene and other aromatic hydrocarbons, propyl ether, isopropyl ether and other ethers, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetic acid Esters such as isobutyl, n-amyl acetate, isoamyl acetate, butyl lactate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, buty
  • Polyoxyalkylene glycol that becomes a hydrophobic liquid at the shell-forming reaction temperature can also be used.
  • polypropylene glycol molecular weight 1000 or more
  • polyoxyethylene-polyoxypropylene block having a proportion of oxyethylene units of less than 20% by mass and a cloud point (1% by mass aqueous solution) of 40°C or less, preferably 20°C or less
  • a copolymer etc. are mentioned.
  • polyoxypropylene-polyoxyethylene-polyoxypropylene type block copolymers are preferably used. These may be used alone or in combination of two or more to the extent that an oil phase is formed in a single phase.
  • hydrocarbons having 8 to 16 carbon atoms, particularly 9 to 12 carbon atoms are preferable.
  • the organic liquid is selected by comprehensively considering operability, safety against fire, separability between the hollow silica precursor and the organic liquid, shape characteristics of the hollow silica particles, solubility of the organic liquid in water, etc. be.
  • Hydrocarbons having 8 to 16 carbon atoms may be linear, branched or cyclic hydrocarbons as long as they have good chemical stability, and hydrocarbons having different carbon atoms may be mixed and used. good too.
  • a saturated hydrocarbon is preferable, and a linear saturated hydrocarbon is more preferable.
  • the flash point of the organic liquid is preferably 20°C or higher, more preferably 40°C or higher. When using an organic liquid with a flash point of less than 20° C., the flash point is too low, so fire prevention and work environment measures are required.
  • Emulsions contain surfactants to enhance emulsion stability.
  • the surfactant is preferably water-soluble or water-dispersible, and is preferably used by being added to the aqueous phase.
  • Nonionic surfactants are preferred.
  • Examples of nonionic surfactants include the following surfactants.
  • polyoxyethylene-polyoxypropylene copolymer surfactant Polyoxyethylene sorbitan fatty acid ester surfactant: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate , Polyoxyethylene higher alcohol ether surfactants: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, Polyoxyethylene aliphatic ester surfactants: polyoxyethylene glycol monolaurate, polyoxyethylene glycol monostearate, polyoxyethylene glycol monooleate, Glycerin fatty acid ester-based surfactants: stearic acid monoglyceride, oleic acid monoglyceride.
  • polyoxyethylene sorbitol fatty acid ester surfactants sucrose fatty acid ester surfactants, polyglycerin fatty acid ester surfactants, polyoxyethylene hydrogenated castor oil surfactants, and the like may be used. These may be used alone or in combination of two or more.
  • a polyoxyethylene-polyoxypropylene copolymer is a block copolymer in which a polyoxyethylene block (EO) and a polyoxypropylene block (PO) are combined.
  • Block copolymers include EO-PO-EO block copolymers, EO-PO block copolymers, etc., and EO-PO-EO block copolymers are preferred.
  • the proportion of oxyethylene units in the EO-PO-EO block copolymer is preferably 20% by mass or more, more preferably 30% by mass or more.
  • the weight average molecular weight of the polyoxyethylene-polyoxypropylene copolymer is preferably 3,000 to 27,000, more preferably 6,000 to 19,000.
  • the total amount of polyoxyethylene blocks is preferably 40 to 90% by mass, and the total amount of polyoxypropylene blocks is preferably 10 to 60% by mass, based on the entire polyoxyethylene-polyoxypropylene copolymer.
  • the amount of surfactant used depends on conditions such as the type of surfactant, HLB (hydrophile-lipophile balance), which is an indicator of the degree of hydrophilicity or hydrophobicity of the surfactant, and the desired particle size of the silica particles.
  • HLB hydrophile-lipophile balance
  • the content in the aqueous phase is preferably 500 to 20,000 mass ppm, more preferably 1,000 to 10,000 mass ppm.
  • the emulsion can be further stabilized.
  • the amount of surfactant remaining in the hollow silica particles can be reduced.
  • the water phase and the oil phase may be blended at a mass ratio of 200:1 to 5:1, preferably 100:1 to 9:1.
  • the method for producing the oil-in-water emulsion is not limited to the following. It can be prepared by preparing an aqueous phase and an oil phase in advance, adding the oil phase to the aqueous phase, and sufficiently mixing or stirring the mixture. Furthermore, methods such as ultrasonic emulsification, stirring emulsification, and high-pressure emulsification that give a physically strong shearing force can be applied.
  • a membrane emulsification method in which an oil phase finely divided through a membrane with fine pores is dispersed in an aqueous phase
  • a phase inversion emulsification method in which a surfactant is dissolved in an oil phase and then an aqueous phase is added to emulsify
  • an interface There is a method such as a phase inversion temperature emulsification method that utilizes the fact that the activator changes from water-soluble to oil-soluble at a temperature near the cloud point.
  • the oil phase is sufficiently dispersed and emulsified in the aqueous phase in order to reduce the particle size of the resulting hollow silica particles and narrow the particle size distribution.
  • the mixture can be emulsified using a high pressure homogenizer at a pressure of 10 bar or higher, preferably 20 bar or higher.
  • a step of aging the obtained oil-in-water emulsion is provided.
  • the fine emulsion preferentially grows, the primary particle size of the obtained hollow silica becomes uniform, and the primary particle size distribution becomes narrow. This makes it possible to reduce the product (A ⁇ B) of the Ar density and the BET specific surface area.
  • the aging time is 0.5-240 hours. When the aging time is 0.5 hours or more, the uniformity of the particle size of the primary particles is enhanced, and when it is 240 hours or less, the productivity is good.
  • the aging time is preferably 0.5-96 hours, most preferably 0.5-48 hours.
  • the aging temperature is preferably 5 to 80°C, more preferably 20 to 70°C, most preferably 20 to 55°C.
  • the first silica raw material is added to the oil-in-water emulsion.
  • the first silica raw material is selected from, for example, an aqueous solution in which water-soluble silica is dissolved, an aqueous dispersion in which solid silica is dispersed, a mixture thereof, and the group consisting of alkali metal silicate, active silicic acid and silicon alkoxide. or an aqueous solution or dispersion thereof.
  • alkali metal silicates, active silicic acid and silicon alkoxides, or aqueous solutions or aqueous dispersions thereof are preferred from the viewpoint of high availability.
  • Examples of solid silica include silica sol obtained by hydrolyzing an organosilicon compound and commercially available silica sol.
  • Examples of the alkali metal of the alkali metal silicate include lithium, sodium, potassium, rubidium, etc. Among them, sodium is preferred from the standpoint of availability and economic reasons. That is, sodium silicate is preferable as the alkali metal silicate.
  • Sodium silicate has a composition represented by Na2O.nSiO2.mH2O .
  • the ratio of sodium to silicic acid is preferably 1.0 to 4.0, more preferably 2.0 to 3.5 in terms of Na 2 O/SiO 2 molar ratio n.
  • Activated silicic acid is obtained by subjecting an alkali metal silicate to a cation exchange treatment to replace the alkali metal with hydrogen, and an aqueous solution of this activated silicic acid exhibits weak acidity.
  • a hydrogen type cation exchange resin can be used for cation exchange.
  • the alkali metal silicate and active silicic acid are preferably dissolved or dispersed in water before being added to the emulsion.
  • the concentration of the alkali metal silicate and active silicic acid aqueous solution is preferably 3 to 30% by mass, more preferably 5 to 25% by mass in terms of SiO 2 concentration.
  • tetraalkylsilanes such as tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane can be preferably used.
  • Composite particles can also be obtained by mixing other metal oxides and the like with the silica raw material.
  • Other metal oxides include titanium dioxide, zinc oxide, cerium oxide, copper oxide, iron oxide, tin oxide, and the like.
  • the above silica raw materials can be used alone or in combination of two or more. Among them, it is preferable to use an alkali metal silicate aqueous solution, particularly a sodium silicate aqueous solution, as the first silica raw material.
  • the addition of the first silica raw material to the oil-in-water emulsion is preferably performed under acidic conditions.
  • a silica raw material in an acidic environment silica fine particles are generated and a network is formed to form the first-stage coating.
  • the reaction temperature is preferably 80°C or lower, more preferably 70°C or lower, even more preferably 60°C or lower, particularly preferably 50°C or lower, and most preferably 40°C or lower.
  • the temperature is preferably 4° C. or higher, more preferably 10° C. or higher, further preferably 15° C. or higher, and 20° C. or higher. Especially preferred, 25° C. or higher is most preferred. That is, the reaction temperature is preferably in the range of 4-80°C.
  • the pH of the oil-in-water emulsion is more preferably less than 3, more preferably 2.5 or less, from the viewpoint of making the thickness of the coating more uniform and making the silica shell layer of the obtained hollow silica more dense. , more preferably 1 or more. That is, the pH of the oil-in-water emulsion is preferably in the range of 1 or more and less than 3.
  • Acids include, for example, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, perchloric acid, hydrobromic acid, trichloroacetic acid, dichloroacetic acid, methanesulfonic acid, and benzenesulfonic acid.
  • the amount of the first silica raw material added is 1 to 50 parts by mass of SiO 2 in the first silica raw material with respect to 100 parts by mass of the oil phase contained in the emulsion. , more preferably 3 to 30 parts by mass.
  • the pH of the emulsion is maintained acidic, and is preferably held for 1 minute or more, more preferably 5 minutes or more, and further preferably 10 minutes or more. preferable.
  • the pH of the emulsion to which the first silica raw material is added is kept at 3 or more and 7 or less (weakly acidic to neutral). This allows the first silica raw material to be immobilized on the surface of the oil droplets.
  • the pH of the emulsion is adjusted to 3 or more by adding a base to the emulsion to which the first silica raw material is added.
  • Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, ammonia, and amines.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide
  • ammonia and amines.
  • a method of exchanging anions such as halogen ions with hydroxide ions by anion exchange treatment may be used.
  • the base When adding the base, it is preferable to gradually increase the pH of the emulsion by gradually adding the base while stirring the emulsion to which the first silica raw material has been added. If the stirring is weak or if a large amount of base is added at once, the pH of the emulsion will become uneven and the thickness of the first layer coating will become uneven.
  • the holding temperature is preferably 100° C. or lower for maintaining the stability of the emulsion, more preferably 95° C. or lower, even more preferably 90° C. or lower, and particularly preferably 85° C. or lower.
  • the holding temperature is preferably 35°C or higher, more preferably 40°C or higher, and particularly preferably 45°C or higher. That is, the holding temperature of the emulsion is preferably in the range of 35-100°C.
  • a second silica raw material is added to the emulsion in the presence of alkali metal ions.
  • the hollow silica precursor is an oil core-silica shell particle.
  • Addition of the second silica raw material to the emulsion is preferably carried out under alkaline conditions.
  • the emulsion in order to make the adhesion of the first silica raw material to the oil droplets more uniform, the emulsion is once acidified and then the pH is adjusted to 3 or more and 7 or less (weakly acidic to neutral). method.
  • the first silica layer obtained by this method is porous and insufficiently dense, resulting in low strength.
  • the second silica raw material by making the emulsion alkaline, a high-density second silica layer can be formed on the previously obtained first silica layer.
  • the pH of the emulsion when adding the second silica raw material is preferably 8 or higher, more preferably 8.5 or higher, further preferably 8.7 or higher, in order to suppress the generation of new fine particles. 9 or more is particularly preferred, and 9 or more is most preferred. Also, if the pH is too high, the solubility of silica increases, so it is preferably 13 or less, more preferably 12.5 or less, even more preferably 12 or less, particularly preferably 11.5 or less, and most preferably 11 or less. preferable. That is, the pH of the emulsion is preferably in the range of 8-13.
  • Addition of a base can be used to make the pH of the oil-in-water emulsion alkaline.
  • the same compounds as those mentioned above are used.
  • the same one as the first silica raw material described above can be used alone, or two or more kinds can be used in combination.
  • at least one of the sodium silicate aqueous solution and the active silicic acid aqueous solution is preferably used for addition of the second silica raw material.
  • a method of adding an alkali metal hydroxide simultaneously with the second silica raw material may be used.
  • a method using sodium silicate as an alkali metal silicate for the second silica raw material may be used.
  • sodium silicate which is an alkaline component
  • the pH of the emulsion is made alkaline while adding the second silica raw material. can hold. Also, alkali metal ions become present in the emulsion.
  • an acid may be added to adjust the pH.
  • the acid used here the same acid as that used when adding the first silica raw material may be used.
  • the second silica raw material is preferably added in the presence of alkali metal ions.
  • the alkali metal ions may be derived from the first silica raw material, from the second silica raw material, or from the base added for pH adjustment, and can also be blended by adding additives to the emulsion.
  • an alkali metal silicate is used for at least one of the first silica raw material and the second silica raw material.
  • alkali metal halides, sulfates, nitrates, fatty acid salts, and the like are used as additives for the emulsion.
  • the sodium silicate aqueous solution and the active silicic acid aqueous solution may be added to the emulsion after addition of the first silica raw material.
  • the sodium silicate aqueous solution and the activated silicic acid aqueous solution may be added all at once, or may be added in order.
  • the addition of the second silica raw material includes a step of adding a sodium silicate aqueous solution to promote adhesion of the silica raw material on the first silica layer while adjusting the pH, and an active silicic acid aqueous solution. can be performed once or repeated two or more times.
  • the second silica raw material is preferably added to the heated emulsion in order to promote adhesion of the silica raw material onto the first silica layer.
  • the temperature of the emulsion is preferably 30° C. or higher, more preferably 35° C. or higher, even more preferably 40° C. or higher, particularly preferably 45° C. or higher, and most preferably 50° C. or higher, in order to suppress generation of new fine particles. If the temperature is too high, the solubility of silica increases. Therefore, the temperature is preferably 100°C or lower, more preferably 95°C or lower, even more preferably 90°C or lower, particularly preferably 85°C or lower, and most preferably 80°C or lower.
  • the temperature of the emulsion when adding the second silica raw material is preferably in the range of 30 to 100.degree.
  • the amount of the second silica raw material added is adjusted so that SiO 2 in the second silica raw material is 20 to 500 parts by mass with respect to 100 parts by mass of the oil phase. and more preferably adjusted to 40 to 300 parts by mass.
  • the total amount of the first silica raw material and the second silica raw material added is the first silica raw material with respect to 100 parts by mass of the oil phase
  • the total amount of SiO 2 in the inside and SiO 2 in the second silica raw material is preferably adjusted to 30 to 500 parts by mass, more preferably 50 to 300 parts by mass.
  • the silica shell layer of the present invention is mainly composed of silica, but may contain other metal components such as Ti and Zr as necessary for adjusting the refractive index.
  • the method of adding other metal components is not particularly limited, for example, a method of simultaneously adding a metal sol liquid or an aqueous metal salt solution in the step of adding the silica raw material is used.
  • a hollow silica precursor dispersion is obtained as described above.
  • Methods for obtaining a hollow silica precursor from a hollow silica precursor dispersion include, for example, a method of filtering the dispersion, a method of heating to remove the aqueous phase, a method of separating the precursor by sedimentation or centrifugation, and the like. be. As an example, there is a method of filtering the dispersion using a filter of about 0.1 ⁇ m to 5 ⁇ m and drying the filtered hollow silica precursor.
  • the obtained hollow silica precursor may be washed with water, an acid, an alkali, an organic solvent, or the like.
  • the hollow silica precursor is heat-treated after removing the oil core.
  • a method for removing the oil core for example, a method of calcining a hollow silica precursor and burning and decomposing the oil, a method of volatilizing the oil by drying, a method of adding an appropriate additive to decompose the oil, and using an organic solvent.
  • a method of extracting oil by using Among them a method of firing a hollow silica precursor with little oil residue to decompose the oil by combustion is preferable.
  • the first heat treatment removes the organic components of the oil core and surfactant. Since it is necessary to thermally decompose the oil in the hollow silica precursor, the temperature is preferably 100° C. or higher, more preferably 200° C. or higher, and most preferably 300° C. or higher. If the heat treatment in the first step is too high, the silica shell will become denser and it will become difficult to remove the internal organic components. 520° C. or lower is more preferable, 510° C. or lower is particularly preferable, and 500° C. or lower is most preferable. That is, the temperature of the heat treatment in the first stage is preferably in the range of 100°C or more and less than 700°C. The heat treatment in the first stage may be performed once or may be performed multiple times.
  • the first heat treatment time is preferably 30 minutes or longer, preferably 1 hour or longer, more preferably 2 hours or longer, and preferably 48 hours or shorter, more preferably 24 hours or shorter, and more preferably 12 hours or shorter. That is, the first heat treatment time is preferably in the range of 30 minutes to 48 hours.
  • the hollow silica particles are baked to densify the shell, reduce the surface silanol groups, and lower the dielectric loss tangent.
  • the firing temperature in the second stage is preferably higher than the heat treatment temperature in the first stage.
  • the temperature is preferably 700° C. or higher, more preferably 800° C. or higher, still more preferably 900° C. or higher, and most preferably 1000° C. or higher.
  • the temperature of the heat treatment in the second step is in the range of 700 to 1200.degree.
  • the temperature of the heat treatment in the second stage is preferably higher than that in the first stage by 200° C. or more, more preferably 200 to 800° C., and even more preferably 400 to 700° C. higher.
  • the heat treatment in the second stage may be performed once or may be performed multiple times.
  • the second-stage heat treatment time when the standing method is used is preferably 10 minutes or longer, more preferably 30 minutes or longer, and preferably 24 hours or shorter, more preferably 12 hours or shorter, and most preferably 6 hours or shorter. That is, the second heat treatment time is preferably in the range of 10 minutes to 24 hours.
  • a spray combustion method may be used for the second heat treatment.
  • the flame temperature at that time is preferably 1000° C. or higher, preferably 1200° C. or higher, most preferably 1400° C. or higher.
  • the flame temperature is preferably 2000° C. or lower, more preferably 1800° C. or lower, and most preferably 1600° C. or lower. That is, the temperature of the second heat treatment in the spray combustion method is preferably in the range of 1000 to 2000.degree.
  • the hollow silica precursor may be returned to room temperature before performing the second-step heat treatment, or the temperature of the second-step heat treatment may be raised from the state where the first-step calcination temperature is maintained. You can warm it.
  • the fired hollow silica particles after the heat treatment obtained in the above step may be surface-treated with a silane coupling agent.
  • the silanol groups present on the surface of the fired hollow silica particles react with the silane coupling agent, the amount of surface silanol groups is reduced, and the dielectric loss tangent can be reduced.
  • the surface is made hydrophobic and the affinity for the resin is improved, the dispersibility in the resin is improved.
  • surface treatment conditions there are no particular restrictions on the surface treatment conditions, general surface treatment conditions may be used, and wet treatment methods and dry treatment methods are used. A wet processing method is preferable from the viewpoint of uniform processing.
  • Silane coupling agents used for surface treatment include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, and organosilazane compounds. These may be used singly or in combination of two or more.
  • surface treatment agents include aminosilanes such as aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and N-2(aminoethyl)aminopropyltrimethoxysilane.
  • Epoxysilane-based coupling agents such as mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane; methyltrimethoxysilane, vinyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacryloxypropyl Silane - based coupling agents such as trimethoxysilane, imidazolesilane , and triazinesilane ; CF3 ( CF2 ) 7CH2CH2Si ( OCH3 ) 3 , CF3 ( CF2 ) 7CH2CH2SiCl3 , CF 3 ( CF2 ) 7CH2CH2Si ( CH3 ) ( OCH3 ) 2 , CF3 ( CF2 ) 7CH2CH2Si ( CH3 ) C12, CF3 ( CF2 ) 5
  • the treatment amount of the silane coupling agent is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and even more preferably 2 parts by mass or more with respect to 100 parts by mass of the hollow silica particles. Moreover, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less. That is, the treatment amount of the silane coupling agent is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the hollow silica particles.
  • Examples of the method of treating with a silane coupling agent include a dry method in which a silane coupling agent is sprayed onto fired hollow silica particles, and a wet method in which the fired hollow silica particles are dispersed in a solvent and then a silane coupling agent is added for reaction. law, etc.
  • the hollow silica particles obtained by the above process may aggregate due to the drying and firing processes, so they may be crushed to an aggregate size that is easy to handle.
  • crushing methods include a method using a mortar, a method using a dry or wet ball mill, a method using a shaking sieve, and crushers such as pin mills, cutter mills, hammer mills, knife mills, roller mills, and jet mills. There are methods such as using
  • the preferable aggregation diameter (specifically, the median diameter and the coarse particle diameter) of the secondary particles are as described above.
  • the hollow silica particles of the present invention have a densified shell layer, so when added to organic solvents such as methyl ethyl ketone and N-methylpyrrolidone, the permeability of various solvents is low. Therefore, the dispersibility in various solvents is good, and the properties peculiar to the hollow particles in the solvent can be maintained.
  • organic solvents such as methyl ethyl ketone and N-methylpyrrolidone
  • the hollow silica particles of the present invention can be used as various fillers, and in particular, electronic devices such as personal computers, laptop computers, digital cameras, and communication devices such as smartphones and game machines.
  • Resin composition used for producing electronic substrates. can be suitably used as a filling material for objects.
  • the silica powder of the present invention is used in resin compositions, prepregs, metal foil-clad laminates, printed wiring boards, resins, etc., for low dielectric constant, low transmission loss, low moisture absorption, and improved peel strength. It is also expected to be applied to sheets, adhesive layers, adhesive films, solder resists, bump reflow, rewiring insulating layers, die bonding materials, sealing materials, underfills, mold underfills, laminated inductors, and the like.
  • Example 1 "Preparation of emulsion" 4 g of EO-PO-EO block copolymer (Pluronic F68 manufactured by ADEKA) was added to 1250 g of pure water and stirred until dissolved. 42 g of n-decane in which 4 g of sorbitan acid monooleate (Ionet S-80 manufactured by Sanyo Kasei Co., Ltd.) was dissolved was added to this aqueous solution, and the mixture was stirred using a homogenizer manufactured by IKA until the entire liquid became uniform to prepare a crude emulsion. This coarse emulsion was emulsified at a pressure of 50 bar using a high-pressure emulsifier (LAB1000 manufactured by SMTE) to prepare a fine emulsion having an emulsion diameter of 1 ⁇ m.
  • LAB1000 high-pressure emulsifier
  • Sphericality Percentage of Particles with a Particle Diameter Within ⁇ 40% of Average Primary Particle Diameter
  • SEM image A scanning electron microscope image (SEM image) of the hollow silica particles obtained in Example 1 is shown in FIG. The SEM image was observed at an acceleration voltage of 5 kV using S4800 manufactured by Hitachi High-Tech.
  • the diameter of the circumscribed circle (DL) and the diameter of the inscribed circle (DS) are measured.
  • the sphericity was obtained from the calculated average value of the ratio (DS/DL).
  • the primary particle diameters of 100 arbitrary particles were measured, and from the distribution obtained by tabulating them, the proportion of particles having a particle diameter within ⁇ 40% of the average primary particle diameter was determined.
  • Viscosity The density of the particles obtained by density measurement with a dry pycnometer using argon gas is A (g/cm 3 ), and 6 parts by mass of boiled linseed oil and hollow silica particles (6 ⁇ A / 2.2) by mass are The kneaded product obtained by mixing and kneading at 2000 rpm for 3 minutes was measured at a shear rate of 1 s ⁇ 1 for 30 seconds using a rotary rheometer to obtain the viscosity at 30 seconds. Table 1 shows the results.
  • each peak of the spectrum after Fourier transform was optimized using the nonlinear least-squares method with variable parameters such as the center position, height, and half width of the peak shape created by mixing Lorentzian and Gaussian waveforms. rice field.
  • Targeting four structural units of Q1, Q2, Q3 and Q4, the molar ratio of Q3 and Q4 was calculated from the obtained Q1 content, Q2 content, Q3 content and Q4 content. Table 1 shows the results.
  • Relative permittivity, dielectric loss tangent are measured using a dedicated device (vector network analyzer "E5063A", manufactured by Keycom Co., Ltd.) using a perturbation resonator method at a test frequency of 1 GHz, a test temperature of about 24°C, Measurements were performed at a humidity of about 45% and three measurements. Specifically, after drying the hollow silica particles in a vacuum at 150 ° C., filling the PTFE cylinder with sufficient tapping of the powder, measuring the relative permittivity of each container, and then using the logarithmic law of mixture The relative permittivity of the powder converted into modulus and dielectric loss tangent. Table 1 shows the results.
  • Example 2 It was carried out under the same conditions as in Example 1 except that 2 g of EO-PO-EO block copolymer ("Pluronic F68" manufactured by ADEKA) and 2 g of sorbitan acid monooleate (Ionet S-80 manufactured by Sanyo Kasei) were changed.
  • 2 g of EO-PO-EO block copolymer (“Pluronic F68” manufactured by ADEKA)
  • 2 g of sorbitan acid monooleate Ionet S-80 manufactured by Sanyo Kasei
  • Example 3 EO-PO-EO block copolymer (“Pluronic F68" manufactured by ADEKA) was changed to 10 g, sorbitan acid monooleate (Ionet S-80 manufactured by Sanyo Kasei) was not used, and emulsification was performed at a pressure of 100 bar. It was carried out under the same conditions as in Example 1.
  • Example 4 The obtained hollow silica precursor was calcined at 1100° C. for 1 hour (heating time 10° C./min) under the same conditions as in Example 1.
  • Example 5 The obtained hollow silica precursor was calcined at 800° C. for 1 hour (heating time: 10° C./min) under the same conditions as in Example 1.
  • Example 6 The obtained hollow silica precursor was calcined at 700° C. for 1 hour (heating time: 10° C./min), but the same conditions as in Example 1 were used.
  • Example 7 The procedure was carried out under the same conditions as in Example 1, except that 350 ml of tap water was added in place of the ion-exchanged water, and the hollow silica cake was washed by pressure filtration again.
  • Example 8 It was carried out under the same conditions as in Example 1, except that no surface treatment was carried out.
  • Example 9 It was carried out under the same conditions as in Example 1, except that the resulting fine emulsion was allowed to stand at 80° C. for 4 hours for aging.
  • Example 10 It was carried out under the same conditions as in Example 1, except that 3 g of EO-PO-EO block copolymer ("Pluronic F68" manufactured by ADEKA) and 5 g of sorbitan acid monooleate (Ionet S-80 manufactured by Sanyo Kasei) were changed.
  • Example 11 The conditions were the same as in Example 1, except that the formation of the first-stage shell and the formation of the second-stage shell were performed as follows.
  • “1st stage shell formation” 0.90 g of methyl orthosilicate and 2M hydrochloric acid were added to 1300 g of the obtained fine emulsion so as to adjust the pH to 2, and the mixture was well stirred while maintaining the temperature at 30°C.
  • 1M aqueous ammonia was slowly added dropwise to this liquid while stirring well so that the pH of the liquid became 6, to obtain an oil core-silica shell particle dispersion liquid.
  • the resulting oil core-silica shell particle dispersion was retained and aged.
  • SO-C2 deflagration silica with a median diameter of 0.5 ⁇ m, solid silica, manufactured by Admatechs
  • SO-C2 deflagration silica with a median diameter of 0.5 ⁇ m, solid silica, manufactured by Admatechs
  • a spray dryer Mini Spray Dryer B290, manufactured by Nihon Buchi Co., Ltd.
  • This precursor silica was calcined at 1300° C. to obtain hollow silica particles having a space inside.
  • Example 13 The hollow silica precursor obtained in Example 1 was used as is without calcination.
  • Example 15 iM16K (glass balloon with a median diameter of 18 ⁇ m, manufactured by 3M) was used as it was.
  • Examples 1 to 12 had a low dielectric constant at 1 GHz
  • Example 14 had a high dielectric constant at 1 GHz, and the desired effect of the present invention could not be obtained. This is probably because the presence of spaces inside the silica particles of Examples 1 to 12 lowered the relative permittivity by the air content.
  • Examples 13 and 15 had a large dielectric loss tangent at 1 GHz, and the intended effects of the present invention could not be obtained. This is probably because the hollow silica of Example 13 has a large value of Ar density x BET specific surface area and a large value of Q3/Q4, which tends to increase the number of silanol groups contained in the silica, which deteriorates the dielectric loss tangent. Further, it is considered that the dielectric loss tangent of Example 15 deteriorated because of glass balloons instead of silica, which tended to contain many alkaline components and many silanol groups.
  • a release-treated transparent polyethylene terephthalate (PET) film (“PET5011 550” manufactured by Lintec Corporation, thickness 50 ⁇ m) was prepared. Using an applicator, the obtained varnish was applied to the release-treated surface of the PET film so that the thickness after drying was 40 ⁇ m, dried in a gear oven at 100 ° C. for 10 minutes, then cut and cut lengthwise. An uncured laminate film comprising an uncured resin film (B stage film) of 200 mm ⁇ 200 mm wide ⁇ 40 ⁇ m thick was produced. The resulting uncured laminated film was heated in a gear oven at 190° C. for 90 minutes to cure the uncured resin film, thereby producing a resin film.
  • PET transparent polyethylene terephthalate
  • evaluation 1. Evaluation of Relative Permittivity and Dielectric Loss Tangent
  • the relative permittivity and dielectric loss tangent (measurement frequency: 10 GHz) were measured with a vertical split post dielectric resonator (manufactured by Agilent Technologies). Table 2 shows the results.
  • the evaluation sample A was cut into a size of 3 mm ⁇ 25 mm. This sample was heated using a thermomechanical analyzer ("TMA-60" manufactured by Shimadzu Corporation) under a load of 5N and a temperature increase rate of 2°C/min. Then, the dimensional change of the sample was measured from 30° C. to 150° C., and the average coefficient of linear expansion (ppm/° C.) was obtained by dividing the dimensional change of the long side by the temperature. Table 2 shows the results.
  • Example 14 When solid silica was used as in Example 14, the dielectric constant was high and the peel strength was poor.
  • borosilicate glass balloons are used as in Example 15, the dielectric loss tangent is high due to the large amount of surface silanol due to the alkali content contained in the borosilicate glass, and the thermal expansion coefficient of borosilicate glass is higher than that of silica. Therefore, it was found that the average coefficient of linear expansion also increased.

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