Classifications

• • 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
  • C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
• • 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
  • 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
  • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
  • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
• • 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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
• • C—CHEMISTRY; METALLURGY
  • 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
  • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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  • 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
• • 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
  • 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
  • C01P2006/40—Electric properties

Definitions

• the present invention relates to a spherical silica powder and a method for producing the spherical silica powder.
• Silica particles containing silica (SiO 2 ) as a main component have conventionally been used in a variety of applications, including electronic materials such as printed wiring boards and package wiring boards, optical materials such as lenses and optical films, functional materials such as catalysts and catalyst carriers, and pigments for paints and cosmetics.
• Silica has a low dielectric constant (3.9) and a low thermal expansion coefficient (3-7.9 ppm/°C), making it a promising filler material with both a low dielectric constant and a low thermal expansion coefficient, and it is expected to be used in high-frequency dielectric devices.
• Patent Document 1 examines the reduction of the amount of silanol groups by baking silica containing silanol groups at a temperature of 1100°C or higher in a hydrogen gas flow.
• the objective of the present invention is to provide a spherical silica powder that has low dielectric loss and excellent adhesion to resin when mixed with resin for use in electronic applications.
• the present invention relates to the following: [1] A spherical silica powder, in which the ratio (B/A) of a maximum IR peak intensity A at 3600 to 3700 cm ⁇ 1 originating from an internal silanol group of the spherical silica powder to a maximum IR peak intensity B at more than 3700 cm ⁇ 1 and not more than 3800 cm ⁇ 1 originating from an isolated silanol group on the surface is 0.5 to 1.5. [2] The spherical silica powder according to [1], wherein the maximum IR peak intensity B at more than 3700 cm -1 and not more than 3800 cm -1 , which is derived from isolated silanol groups on the surface, is 0.1 or less.
• a resin composition comprising the spherical silica powder according to any one of [1] to [8] and a resin.
• the present invention provides spherical silica powder that has low dielectric loss and excellent adhesion to resin when mixed with resin for use in electronic applications.
• the spherical silica powder of the present invention is characterized in that the ratio (B/A) of the maximum IR peak intensity A at 3600 to 3700 cm ⁇ 1 originating from internal silanol groups of the spherical silica powder to the maximum IR peak intensity B at more than 3700 cm ⁇ 1 and not more than 3800 cm ⁇ 1 originating from isolated silanol groups on the surface is 0.5 to 1.5.
• silanol groups (Si-OH) of silica particles are classified into internal silanol groups present in the Si-O network inside the particles, isolated silanol groups present on the particle surface that are not bonded to water adsorbed to the silica particles, and bonded silanol groups that are bonded to water adsorbed to the silica particles or silanol on the silica surface. Since the silanol group, which is a polar functional group, causes an increase in dielectric loss, it is preferable to have a smaller amount of silanol groups from the viewpoint of reducing dielectric loss.
• the present inventors have found that the fewer the isolated silanol groups present on the particle surface, the more inactive the surface of the spherical silica powder becomes, so that the compatibility when mixed with a resin becomes poor, and the adhesion to the resin decreases.
• a spherical silica powder can be provided that has low dielectric loss and excellent adhesion to resin when mixed with resin for use in electronic applications.
• the maximum IR peak intensity A at 3600 to 3700 cm ⁇ 1 derived from the internal silanol groups is preferably less than 0.2.
• the dielectric loss tends to increase when a resin composition in which the spherical silica powder is mixed with a resin is used for electronic applications.
• the maximum IR peak intensity A at 3600 to 3700 cm ⁇ 1 derived from the internal silanol groups of the spherical silica powder is less than 0.2, the dielectric loss can be reduced.
• the maximum IR peak intensity A at 3600 to 3700 cm ⁇ 1 derived from the internal silanol groups is more preferably 0.10 or less, even more preferably 0.08 or less, and most preferably 0.05 or less.
• the internal silanol groups do not interact with the resin and deteriorate the dielectric loss tangent, so it is preferable that they are small. Therefore, the lower limit is not particularly limited.
• the maximum IR peak intensity B at more than 3700 cm -1 and not more than 3800 cm -1 derived from the isolated silanol groups on the surface is preferably 0.1 or less.
• the dielectric loss tends to increase when a resin composition in which the spherical silica powder is mixed with a resin is used for electronic applications, but when the maximum IR peak intensity B at more than 3700 cm -1 and not more than 3800 cm -1 derived from the isolated silanol groups on the surface of the spherical silica powder is 0.1 or less, the dielectric loss can be reduced.
• the maximum IR peak intensity B at more than 3700 cm -1 and not more than 3800 cm -1 derived from the isolated silanol groups on the surface is more preferably 0.05 or less, and even more preferably 0.03 or less. Furthermore, from the viewpoint of improving adhesion to a resin when the spherical silica powder is mixed with the resin, the maximum IR peak intensity B at more than 3700 cm -1 and not more than 3800 cm -1 , which is derived from an isolated silanol group on the surface of the spherical silica powder, is preferably 0.005 or more, more preferably 0.010 or more, even more preferably 0.013 or more, and particularly preferably 0.015 or more. That is, the maximum IR peak intensity B at more than 3700 cm -1 and not more than 3800 cm -1 originating from an isolated silanol group on the surface is preferably in the range of 0.005 to 0.1.
• the spherical silica powder of the present invention has a ratio (B/A) of the maximum IR peak intensity A at 3600 to 3700 cm ⁇ 1 derived from the internal silanol group to the maximum IR peak intensity B at more than 3700 cm ⁇ 1 and not more than 3800 cm ⁇ 1 derived from the isolated silanol group on the surface, which is 0.5 to 1.5.
• B/A is preferably 1.3 or less, more preferably 1.1 or less, and is preferably 0.6 or more, more preferably 0.7 or more.
• the ratio (B/A) of the maximum IR peak intensity A at 3600 to 3700 cm ⁇ 1 originating from internal silanol groups to the maximum IR peak intensity B at more than 3700 cm ⁇ 1 and not more than 3800 cm ⁇ 1 originating from isolated silanol groups on the surface can be adjusted by the firing conditions during production of the spherical silica powder, the particle size of the silica precursor, etc.
• the spherical silica powder of the present invention preferably has a sum (A+B) of the maximum IR peak intensity A at 3600 to 3700 cm ⁇ 1 derived from the internal silanol group and the maximum IR peak intensity B at more than 3700 cm ⁇ 1 and not more than 3800 cm ⁇ 1 derived from the isolated silanol group on the surface, which is less than 0.2.
• A+B is more preferably 0.19 or less, even more preferably 0.15 or less, particularly preferably 0.10 or less, and most preferably 0.05 or less. From the viewpoint of improving the adhesion at the interface between the isolated silanol groups on the silica surface and the resin, A+B is preferably 0.02 or more, and more preferably 0.03 or more.
• the maximum IR peak intensity at 3300 to 3800 cm ⁇ 1 derived from the silanol groups of the spherical silica powder is preferably 0.2 or less, more preferably 0.1 or less, even more preferably 0.05 or less, particularly preferably 0.02 or less, and most preferably 0.017 or less. If the maximum IR peak intensity at 3300 to 3800 cm ⁇ 1 is 0.2 or less, the dielectric loss can be reduced when a resin composition in which the spherical silica powder is mixed is used for electronic applications.
• the maximum IR peak intensity at 3300 to 3800 cm ⁇ 1 originating from the silanol groups of the spherical silica powder is preferably 0.010 or more.
• the IR spectrum of the silanol groups of the spherical silica powder can be measured by the following procedure. (Measurement method) Using an infrared spectrometer (for example, IR Prestige-21 (manufactured by Shimadzu Corporation)), spherical silica powder is dispersed in diamond and measured by the diffuse reflectance method. The measurement range is 400 to 4000 cm -1 , the resolution is 4 cm -1 , and the number of integrations is 128.
• Measurement method Using an infrared spectrometer (for example, IR Prestige-21 (manufactured by Shimadzu Corporation)), spherical silica powder is dispersed in diamond and measured by the diffuse reflectance method. The measurement range is 400 to 4000 cm -1 , the resolution is 4 cm -1 , and the number of integrations is 128.
• the spherical silica powder used is vacuum dried at 180° C. for 1 hour. After normalizing the IR spectrum at 800 cm ⁇ 1 and adjusting the baseline at 3800 cm ⁇ 1 , the maximum IR peak between 3600 and 3700 cm ⁇ 1 , the maximum IR peak between 3700 cm ⁇ 1 and 3800 cm ⁇ 1 , and the maximum IR peak between 3300 and 3800 cm ⁇ 1 are obtained.
• the spherical silica powder preferably has a median diameter d50, which is the particle diameter at the point where the cumulative volume is 50% on a volume-based particle size distribution curve, of 0.5 to 20.0 ⁇ m.
• a median diameter d50 of the spherical silica powder is 0.5 ⁇ m or more, the dielectric loss tangent can be significantly reduced.
• the median diameter d50 of the spherical silica powder is 20.0 ⁇ m or less, the grain gauge value can be prevented from increasing, and therefore, when a resin composition containing the spherical silica powder is used for electronic applications, excellent peel strength can be obtained. Therefore, in the present invention, the median diameter d50 of the spherical silica powder is preferably 0.5 to 20.0 ⁇ m, more preferably 0.5 to 10.0 ⁇ m, and even more preferably 1 to 5.0 ⁇ m.
• the 10% particle size d10 which is the particle size at which the cumulative volume is 10% in the volume-based particle size distribution curve of the spherical silica powder, is preferably 0.5 to 5.0 ⁇ m, and more preferably 1.0 to 3.0 ⁇ m, from the viewpoint of improving the uniform dispersion when the spherical silica powder is mixed into the resin while enhancing the interaction between the spherical silica powder and the resin.
• the ratio of the median diameter d50 to the 10% particle diameter d10 is preferably greater than 1.0 and not greater than 5.0, more preferably 1.3 to 4.0, and even more preferably 1.5 to 3.0, from the viewpoint of improving uniform dispersion when the spherical silica powder is mixed into the resin while enhancing the interaction between the spherical silica powder and the resin.
• the maximum particle diameter (Dmax) of the spherical silica powder is preferably 150 times or less than the median diameter d50, more preferably 100 times or less, even more preferably 50 times or less, and particularly preferably 10 times or less. If the maximum particle diameter (Dmax) is 150 times or less than the median diameter d50, defects are less likely to occur when the sheet is processed. In addition, the maximum particle diameter (Dmax) is preferably 1.2 times or more than the median diameter d50, more preferably 1.5 times or more, and even more preferably 2 times or more.
• the median diameter d50 is a volume-based cumulative 50% diameter determined by a laser diffraction particle size distribution measuring device (e.g., "MT3300EXII” manufactured by Microtrac-Bell Co., Ltd.). That is, the particle size distribution is measured by a laser diffraction/scattering method, a cumulative curve is obtained with the total volume of the spherical silica powder being 100%, and the median diameter d50 is the particle diameter at the point on the cumulative curve where the cumulative volume is 50%.
• the 10% particle diameter d10 is a volume-based cumulative 10% diameter obtained by a laser diffraction particle size distribution measuring device (e.g., "MT3300EXII” manufactured by Microtrac-Bell Co., Ltd.).
• the particle size distribution is measured by a laser diffraction/scattering method, a cumulative curve is obtained with the total volume of the spherical silica powder being 100%, and the 10% particle diameter d10 is the particle diameter at the point on the cumulative curve where the cumulative volume is 10%.
• the maximum particle size can be obtained by the same measurement as the median size d50 and the 10% particle size d10.
• the specific surface area Y of the spherical silica powder of the present invention is preferably in the range of 0.1 to 4.0 m 2 /g. If the specific surface area Y is 0.1 m 2 /g or more, when the spherical silica powder is contained in a resin composition, there is a sufficient contact point with the resin, so that the compatibility with the resin is good, and if the specific surface area Y is 4.0 m 2 /g or less, the dielectric tangent can be made small, so that an excellent low dielectric tangent can be exhibited even in the resin composition, and the dispersibility in the resin composition is improved.
• the specific surface area Y is preferably 4.0 m 2 /g or less, more preferably 3.5 m 2 /g or less, particularly preferably 3.0 m 2 /g or less, and preferably 0.1 m 2 /g or more, more preferably 0.2 m 2 /g or more, and particularly preferably 0.5 m 2 /g or more. It is practically difficult to obtain a specific surface area Y of less than 0.1 m 2 /g.
• the specific surface area is determined by the BET method based on the nitrogen adsorption method using a specific surface area/pore distribution measuring device (e.g., Microtrac-Bell's "BELSORP-mini II” or Micromeritics' “Tristar II”).
• a specific surface area/pore distribution measuring device e.g., Microtrac-Bell's "BELSORP-mini II” or Micromeritics' “Tristar II”
• the product Y ⁇ d50 of the specific surface area Y (m 2 /g) and the median diameter d50 ( ⁇ m) of the spherical silica powder is preferably 2.7 to 5.0 ⁇ m ⁇ m 2 /g.
• Y ⁇ d50 is more preferably 2.7 to 4.5 ⁇ m ⁇ m 2 /g, and even more preferably 2.7 to 4.0 ⁇ m ⁇ m 2 /g.
• the average circularity of the spherical silica powder is preferably 0.75 to 1.0. As the average circularity decreases, the specific surface area increases, and the dielectric tangent tends to increase, so the average circularity is preferably 0.75 or more.
• the average circularity is more preferably 0.85 or more, even more preferably 0.90 or more, and particularly preferably 0.93 or more, and the closer to 1.0 the better.
• the average circularity is obtained by measuring the maximum diameter (DL) and the perpendicular minor diameter (DS) of 100 random particles in a photographic projection obtained by photographing with a scanning electron microscope (SEM), and calculating the average value of the ratio (DS/DL) of the minimum diameter (DS) to the maximum diameter (DL).
• the spherical silica powder of the present invention preferably has a dielectric loss tangent of 0.0020 or less at a frequency of 1 GHz, more preferably 0.0010 or less, and even more preferably 0.0008 or less.
• the sample space becomes small at frequencies of 10 GHz or more, and the measurement accuracy deteriorates, so the measured value at a frequency of 1 GHz is adopted in the present invention.
• the dielectric loss tangent of the spherical silica powder at a frequency of 1 GHz is 0.0020 or less, an excellent dielectric loss suppression effect is obtained, so that a substrate or sheet with improved high frequency characteristics can be obtained.
• the dielectric constant of the spherical silica powder is preferably 5.0 or less, more preferably 4.5 or less, and even more preferably 4.1 or less at a frequency of 1 GHz.
• the dielectric tangent and dielectric constant can be measured using a dedicated device (for example, the "Vector Network Analyzer E5063A" manufactured by Keycom Corporation) using the perturbation resonator method.
• the spherical silica powder of the present invention is preferably one in which the viscosity of a kneaded product containing the spherical silica powder, as measured by the following measurement method, is 5000 mPa ⁇ s or less. (Measurement method) 6 parts by mass of boiled linseed oil and 8 parts by mass of spherical silica powder as specified in JIS K 5421:2000 are mixed and kneaded at 2000 rpm for 3 minutes. The kneaded product is measured using a rotational rheometer at a shear rate of 1 s for 30 seconds to determine the viscosity at the 30 second point.
• the viscosity of the kneaded product at a shear rate of 1 s -1 determined by the above measurement method is 5000 mPa.s or less, the amount of solvent added during molding and film formation of the resin composition containing the spherical silica powder can be reduced, the drying speed can be increased, and productivity can be improved.
• the specific surface area according to the particle size of the silica powder is large, the viscosity tends to increase when added to the resin composition, so in order to suppress the increase in viscosity of the resin composition, it is preferable to reduce the specific surface area of the spherical silica powder of the present invention, for example.
• the viscosity of the kneaded product is more preferably 4000 mPa.s or less, and even more preferably 3500 mPa.s or less.
• the lower limit of the viscosity of the kneaded product at a shear rate of 1 s ⁇ 1 is not particularly limited, since the lower the viscosity, the more the coatability of the resin composition improves and the more the productivity improves.
• the spherical silica powder is preferably non-porous particles. If the particles are porous, the oil absorption will be large, the viscosity in the resin will increase, the surface area will increase, and the amount of silanol (Si-OH) groups on the silica particle surface will increase, which will tend to deteriorate the dielectric tangent.
• the oil absorption is preferably 100 ml/100 g or less, more preferably 70 ml/100 g or less, and most preferably 50 ml/100 g or less. There is no particular lower limit, but it is practically difficult to achieve an oil absorption of 20 ml/100 g or less.
• the spherical silica powder of the present invention preferably contains titanium (Ti) in the range of 30 to 1500 ppm by mass.
• Ti titanium
• the Ti content is more preferably 80 ppm by mass or more, even more preferably 100 ppm by mass or more, and more preferably 1000 ppm by mass or less, and even more preferably 500 ppm by mass or less.
• the Ti content can be measured by inductively coupled plasma (ICP) emission spectrometry after adding perchloric acid and hydrofluoric acid to the silica powder, igniting the mixture to remove the main component silicon.
• ICP inductively coupled plasma
• Ti is an optional component that is included in the production of spherical silica powder. If fine powder is generated due to cracking of silica particles during the production of spherical silica powder, the fine powder will adhere to the surface of the base particle, increasing the specific surface area of the particles. By including Ti during the production of spherical silica powder, it becomes easier to compact during firing. This makes it less likely to crack during post-treatment after firing, so the generation of fine powder can be suppressed, and the number of particles adhering to the surface of the silica base particle can be reduced, thereby suppressing the increase in the specific surface area.
• the spherical silica powder of the present invention may contain impurity elements other than titanium (Ti) as long as the effects of the present invention are not impaired.
• impurity elements other than Ti include Na, K, Mg, Ca, Al, and Fe.
• the total content of alkali metals and alkaline earth metals among the impurity elements is preferably 2000 ppm by mass or less, more preferably 1000 ppm by mass or less, and even more preferably 200 ppm by mass or less.
• the method for producing spherical silica powder according to the present invention includes calcining a spherical silica precursor in a reducing atmosphere.
• porous silica precursor which means that pores are uniformly distributed in the silica precursor.
• porous silica particles it is easier to obtain particles with controlled shape and particle size distribution, compared to particles made by pulverizing and firing a non-porous raw material.
• the pore volume of the silica precursor is preferably in the range of 0.1 to 2.0 ml/g. If the pore volume is 0.1 ml/g or more, the apparent volume of the particles decreases when the silica is made non-porous during firing, resulting in sparse particles that are difficult to sinter, or a powder with weak sintering strength is obtained. If the pore volume is 2.0 ml/g or less, the bulk density of the charge before firing is prevented from becoming too large, improving productivity, and the silica particles shrink sufficiently during firing to sufficiently reduce the specific surface area.
• the pore volume is more preferably 0.3 ml/g or more, even more preferably 0.6 ml/g or more, particularly preferably 0.7 ml/g or more, and more preferably 1.8 ml/g or less, even more preferably 1.5 ml/g or less, and particularly preferably 1.2 ml/g or less.
• the specific surface area of the silica precursor is preferably in the range of 200 to 1000 m 2 /g. If the specific surface area is 200 m 2 /g or more, the surface area after firing can be reduced while suppressing sintering of the particles. Furthermore, if the specific surface area is 1000 m 2 /g or less, the strength of the silica precursor particles is sufficiently high.
• the specific surface area is more preferably 400 m 2 /g or more, even more preferably 500 m 2 /g or more, particularly preferably 700 m 2 /g or more, and more preferably 950 m 2 /g or less, and even more preferably 900 m 2 /g or less.
• the pore volume and specific surface area are determined by the BET method based on the nitrogen adsorption method using a specific surface area/pore distribution measuring device (e.g., Microtrac-Bell's "BELSORP-mini II” or Micromeritics' “Tristar II”).
• a specific surface area/pore distribution measuring device e.g., Microtrac-Bell's "BELSORP-mini II” or Micromeritics' “Tristar II”
• the average pore diameter of the silica precursor is preferably 1.0 to 50.0 nm. If the average pore diameter is 1.0 nm or more, the particles can be made uniformly non-porous all the way to the inside, no air bubbles remain inside, and the dielectric tangent can be lowered. If the average pore diameter is 50.0 nm or less, the silica particles can be densified (reduced specific surface area) by firing without leaving pores, and the dielectric tangent can be lowered.
• the average pore diameter is more preferably 2.0 nm or more, even more preferably 3.0 nm or more, and particularly preferably 4.0 nm or more, and more preferably 40.0 nm or less, even more preferably 30.0 nm or less, and particularly preferably 20.0 nm or less.
• the average pore diameter is determined by the BET method based on the nitrogen adsorption method using a specific surface area/pore distribution measuring device (e.g., Microtrac-Bell's "BELSORP-miniII” or Micromeritics' “Tristar II”).
• a specific surface area/pore distribution measuring device e.g., Microtrac-Bell's "BELSORP-miniII” or Micromeritics' “Tristar II”
• the silica precursor used in the manufacturing method of the present invention is spherical, and its average circularity is preferably 0.90 or more. If the average circularity is 0.90 or more, the particle is essentially spherical, so the surface area of the particle can be reduced, and the active surface is not exposed because the protrusions are not chipped by vibration of the particle, so the silica particles can have a low dielectric constant.
• the average circularity is more preferably 0.92 or more, and particularly preferably 0.95 or more. Also, the closer to a perfect sphere, the more desirable it is, so 1.00 is the most preferable.
• the average circularity can be calculated using the same method as described above.
• the median diameter d50 of the silica precursor which is the particle diameter at the point where the cumulative volume is 50% on the volume-based particle size distribution curve, is preferably 1 to 500 ⁇ m. If the median diameter d50 of the silica precursor is 1 ⁇ m or more, it can be made into spherical particles even after baking to reduce the surface area, and if it is 500 ⁇ m or less, it can be easily used as a filler for resins that are easy to mold.
• the median diameter d50 is more preferably 1.2 ⁇ m or more, even more preferably 1.5 ⁇ m or more, more preferably 100 ⁇ m or less, even more preferably 50 ⁇ m or less, particularly preferably 20 ⁇ m or less, even more preferably 10 ⁇ m or less, and most preferably 5 ⁇ m or less.
• the silica precursor preferably has a weight loss rate of 10% or less when dried at 230° C. for 12 hours. If the weight loss rate is 10% or less, when the silica precursor is fired in a state where the particles are in contact with each other, sintering between the particles is unlikely to occur, and spherical silica powder is easily obtained.
• the weight loss rate is more preferably 9% or less, even more preferably 8% or less, and particularly preferably 6% or less.
• the lower limit is not particularly limited.
• the obtained silica precursor has a high water content and the weight loss rate exceeds 10% when dried for 12 hours at 230° C., it is preferable to dry it until the weight loss rate is 10% or less.
• the drying method include a spray dryer, stationary drying in a dryer, ventilation treatment with dry air, etc.
• the ignition loss of the silica precursor is preferably 5.0 to 15.0% by mass.
• the ignition loss is the sum of the water adhering to the silica precursor and the water generated by condensation of the silanol groups contained in the silica precursor. If the silica precursor has an appropriate number of silanol groups, condensation will proceed during firing, making it easier for the silanol groups to decrease. If the ignition loss is too high, the yield during firing will decrease and productivity will deteriorate, so the ignition loss of the silica precursor is preferably 15.0% by mass or less, more preferably 13.0% by mass or less, and most preferably 12.0% by mass or less. If the ignition loss is too low, silanol groups will tend to remain during firing, so the ignition loss of the silica precursor is preferably 5.0% by mass or more, more preferably 6.0% by mass or more, and most preferably 7.0% by mass or more.
• the ignition loss is calculated according to JIS K0067 (1992) as the mass loss when 1 g of silica precursor is heated and dried at 850°C for 0.5 hours.
• the silica precursor may be obtained by manufacturing, or a commercially available product may be used.
• Examples of commercially available products include H-11, H-31, and H-201 manufactured by AGC Si-Tech Co., Ltd.
• the silica precursor When the silica precursor is obtained by manufacturing, it can be obtained by a method such as a wet method, a granulation method, etc. Among these, it is preferable to form the silica precursor by using a wet method.
• the wet method refers to a method that includes a process of using a liquid silica source and gelling it to obtain a raw material for spherical silica powder.
• the wet method is difficult to produce particles that are significantly smaller than the average particle size, and the specific surface area tends to be small after firing.
• the amount of impurity elements such as titanium can be adjusted by adjusting the impurities in the silica source, and the above-mentioned impurity elements can be uniformly dispersed in the particles.
• the wet method examples include a spray method and an emulsion gelation method.
• the emulsion gelation method includes emulsifying a dispersed phase containing a silica precursor and a continuous phase, and gelling the resulting emulsion to obtain a spherical silica precursor.
• a method of supplying a dispersed phase containing a silica precursor to a continuous phase through a micropore or a porous membrane to prepare an emulsion is preferred. This produces an emulsion with a uniform droplet size, resulting in spherical silica with a uniform particle size.
• a micromixer method or a membrane emulsification method can be used as such an emulsification method.
• the micromixer method is disclosed in International Publication No. 2013/062105.
• the spherical silica powder obtained as described above is amorphous solid silica.
• the spherical silica powder of the present invention is obtained by firing the spherical silica precursor in a reducing atmosphere. It is presumed that firing in a reducing atmosphere promotes the condensation of silanol groups and the reduction of OH groups. This can reduce the amount of isolated silanol groups and internal silanol groups on the surface of the spherical silica powder, and in particular, the amount of internal silanol groups is significantly reduced, so that the dielectric properties can be improved while maintaining adhesion to resin.
• the term "reducing atmosphere" refers to an atmosphere containing hydrogen.
• the hydrogen concentration is preferably 1% by volume or more, more preferably 3% by volume or more, even more preferably 5% by volume or more, and particularly preferably 8% by volume or more.
• the upper limit of the hydrogen concentration is 100% by volume.
• the firing method is not particularly limited, but examples include heat treatment by leaving the material to stand and heat treatment in a rotary furnace.
• a stationary electric furnace for heat treatment by leaving the material to stand, a stationary electric furnace, a roller hearth kiln, a continuous furnace classified as a tunnel furnace, etc. can be used.
• a rotary furnace for heat treatment in a rotary furnace, a horizontal rotary furnace (rotary kiln), a rotary tubular furnace, etc. can be used.
• the firing temperature is preferably 700°C or higher, more preferably 800°C or higher, even more preferably 900°C or higher, and particularly preferably 1000°C or higher.
• the firing temperature is preferably 1600°C or lower, more preferably 1500°C or lower, and even more preferably 1400°C or lower.
• the baking time can be adjusted as appropriate depending on the baking equipment and baking time used, but for example, it is preferable to perform the baking for 0.5 to 50 hours, and more preferably 1 to 10 hours.
• Methods for forming a reducing atmosphere include, for example, a method using reducing gas such as hydrogen gas or carbon monoxide.
• An example of a device for forming a reducing atmosphere is an atmospheric furnace that can use the reducing gas. These devices may be equipped with a heating device, a chamber filled with an inert gas (nitrogen, argon, etc.), a mechanism for creating a vacuum in the chamber, etc., within the furnace, which makes it easier to control the reducing gas.
• Spherical silica powder may be weakly sintered to other particles after firing, in which case it may be crushed. Crushing is preferably performed so that the average circularity of the particles does not fall below 0.90 in order to maintain the surface area and not impair the effects of the present invention. It is also preferable that the surface area does not increase as a result of the crushing process. A large increase in surface area due to the crushing process means that some of the spherical particles have been pulverized or that fine damage has occurred on the surface, generating fine powder. An increase in surface area is undesirable because it leads to an increase in viscosity when the spherical silica powder is dispersed in a resin and a deterioration in the dielectric tangent.
• Crushing can be carried out using a crushing device such as a cyclone mill, jet mill, or impact mill, and crushing can also be carried out using an agate mortar or vibrating sieve.
• a crushing device such as a cyclone mill, jet mill, or impact mill
• crushing can also be carried out using an agate mortar or vibrating sieve.
• the spherical silica powder obtained by firing may be surface-treated with a silane coupling agent. This process causes the silanol groups present on the surface of the spherical silica powder to react with the silane coupling agent, reducing the number of silanol groups on the surface and improving the dielectric tangent. In addition, the surface becomes hydrophobic, improving the affinity for resins, and therefore improving dispersibility in resins.
• the surface treatment conditions there are no particular limitations on the surface treatment conditions, and general surface treatment conditions are sufficient, and wet or dry treatment methods can be used. From the viewpoint of performing uniform treatment, the wet treatment method is preferred.
• Silane coupling agents used in surface treatment include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, fluorine-containing silane coupling agents, organosilazane compounds, etc. These may be used alone or in combination of two or more.
• the surface treatment agent includes aminosilane coupling agents such as aminopropyl methoxysilane, aminopropyl triethoxysilane, ureidopropyl triethoxysilane, N-phenyl aminopropyl trimethoxysilane, and N-2 (aminoethyl) aminopropyl trimethoxysilane; epoxysilane coupling agents such as glycidoxypropyl trimethoxysilane, glycidoxypropyl triethoxysilane, glycidoxypropyl methyl diethoxysilane, glycidyl butyl trimethoxysilane, and (3,4-epoxycyclohexyl) ethyl trimethoxysilane; mercaptosilane coupling agents such as mercaptopropyl trimethoxysilane and mercaptopropyl triethoxysilane; silane coupling agents
• organosilazane compounds such as hexamethyldisilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, and 1,1,3,3,5,5-hexamethylcyclotrisilazane.
• the amount of silane coupling agent used for treatment is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and even more preferably 0.10 parts by mass or more, per 100 parts by mass of spherical silica powder, and is preferably 5 parts by mass or less, and more preferably 2 parts by mass or less.
• Methods for treating with a silane coupling agent include, for example, a dry method in which the silane coupling agent is sprayed onto spherical silica powder, and a wet method in which the spherical silica powder is dispersed in a solvent and then a silane coupling agent is added to cause a reaction.
• the fact that the surface of the spherical silica powder has been treated with a silane coupling agent can be confirmed by detecting peaks due to the substituents of the silane coupling agent using IR.
• the amount of silane coupling agent attached can also be measured by the amount of carbon.
• the spherical silica powder of the present invention has excellent adhesion to resins and therefore excellent mixability with resin compositions.
• the resin composition according to the present embodiment contains the spherical silica powder of the present invention and a resin.
• the content of the spherical silica powder in the resin composition is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, even more preferably 10 to 80% by mass, particularly preferably 10 to 75% by mass, particularly preferably 10 to 70% by mass, and most preferably 15 to 70% by mass.
• the content of the spherical silica powder in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and also preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, particularly preferably 75% by mass or less, and most preferably 70% by mass or less.
• the resin one or more of the following can be used: epoxy resin, silicone resin, phenol resin, melamine resin, urea resin, unsaturated polyester resin, fluororesin, polyamide resin such as polyimide resin, polyamideimide resin, polyetherimide; polyester resin such as polybutylene terephthalate, polyethylene terephthalate; polyphenylene ether resin, polyphenylene sulfide resin, orthodivinylbenzene resin, aromatic polyester resin, polysulfone, liquid crystal polymer, polyethersulfone, polycarbonate, maleimide modified resin, ABS (acrylonitrile butadiene styrene) resin, AAS (acrylonitrile-acrylic rubber styrene) resin, AES (acrylonitrile ethylene propylene diene rubber styrene) resin, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), te
• the resin preferably contains a thermosetting resin.
• One type of thermosetting resin may be used, or two or more types may be used.
• thermosetting resins include epoxy resins, polyphenylene ether resins, polyimide resins, phenolic resins, and orthodivinylbenzene resins. From the standpoint of adhesion, heat resistance, and the like, the thermosetting resin is preferably an epoxy resin, polyphenylene ether resin, or orthodivinylbenzene resin.
• the weight average molecular weight of the thermosetting resin is preferably 1000 to 7000, more preferably 1000 to 5000, and even more preferably 1000 to 3000.
• the weight average molecular weight is determined using gel permeation chromatography (GPC) in terms of polystyrene.
• the content of spherical silica powder per 100 parts by mass of thermosetting resin is preferably 10 to 400 parts by mass, more preferably 50 to 300 parts by mass, and even more preferably 70 to 250 parts by mass.
• the content of the silica particles is preferably 80 parts by mass or more, and more preferably 90 parts by mass or more.
• the particle size distribution of the silica particles contained in the resin composition is unimodal.
• the fact that the particle size distribution of the silica particles is unimodal can be confirmed by the fact that there is one peak in the particle size distribution measured by the laser diffraction/scattering method.
• the resin composition may contain optional components other than the above resin and medium (e.g., toluene, methyl ethyl ketone, etc.).
• Optional components include, for example, dispersing agents, surfactants, and fillers other than silica.
• the dielectric tangent is preferably 0.012 or less at a frequency of 10 GHz, more preferably 0.010 or less, and even more preferably 0.009 or less. If the dielectric tangent of the resin film at a frequency of 10 GHz is 0.012 or less, the electrical properties are excellent, and it is expected to be used in electronic devices, communication devices, etc. The smaller the dielectric tangent, the more the transmission loss in the circuit is suppressed, so there is no particular limit to the lower limit.
• the relative dielectric constant is preferably 2.0 to 3.5 at a frequency of 10 GHz, with the lower limit being more preferably 2.2 or more, and even more preferably 2.3 or more, and the upper limit being more preferably 3.2 or less, and even more preferably 3.0 or less.
• the relative dielectric constant of a resin film at a frequency of 10 GHz is within the above range, the resin film has excellent electrical properties, and is therefore expected to be useful in electronic devices, communication devices, and the like.
• the relative dielectric constant can be measured by a perturbation resonator method using a dedicated device (for example, "Vector Network Analyzer E5063A” manufactured by Keycom Corporation).
• the dielectric loss tangent of the resin film can be measured using a split post dielectric resonator (SPDR) (eg, manufactured by Agilent Technologies).
• SPDR split post dielectric resonator
• the resin film preferably has an average linear expansion coefficient of 10 to 50 ppm/°C.
• the average linear expansion coefficient is more preferably 12 ppm/°C or more, even more preferably 15 ppm/°C or more, and more preferably 40 ppm/°C or less, and even more preferably 30 ppm/°C or less.
• the average linear expansion coefficient is determined by using a thermomechanical analyzer (e.g., Shimadzu Corporation's "TMA-60") to heat the resin film with a load of 5 N at a heating rate of 2°C/min, measuring the dimensional change of the sample from 30°C to 150°C, and calculating the average.
• a thermomechanical analyzer e.g., Shimadzu Corporation's "TMA-60”
• the spherical silica powder of the present invention can be used as various fillers, and is particularly suitable as a filler for resin compositions used in the manufacture of electronic substrates for use in electronic devices such as personal computers, notebook computers, and digital cameras, and communication devices such as smartphones and game consoles.
• the silica powder of the present invention is expected to be applied to resin compositions, prepregs, metal foil-clad laminates, printed wiring boards, resin sheets, adhesive layers, adhesive films, solder resists, bump reflow, rewiring insulating layers, die bond materials, encapsulants, underfills, mold underfills, and laminated inductors, etc., in order to reduce dielectric tangent, transmission loss, moisture absorption, and improve peel strength.
• ⁇ 1> A spherical silica powder, in which the ratio (B/A) of a maximum IR peak intensity A at 3600 to 3700 cm ⁇ 1 originating from an internal silanol group of the spherical silica powder to a maximum IR peak intensity B at more than 3700 cm ⁇ 1 and not more than 3800 cm ⁇ 1 originating from an isolated silanol group on the surface is 0.5 to 1.5.
• ⁇ 3> The spherical silica powder according to ⁇ 1> or ⁇ 2>, wherein the sum (A+B) of a maximum IR peak intensity A at 3600 to 3700 cm - 1 derived from an internal silanol group of the spherical silica powder and a maximum IR peak intensity B at more than 3700 cm- 1 and not more than 3800 cm-1 derived from an isolated silanol group on the surface is less than 0.2.
• ⁇ 4> The spherical silica powder according to any one of ⁇ 1> to ⁇ 3>, wherein the maximum IR peak intensity at 3300 to 3800 cm ⁇ 1 derived from silanol groups of the spherical silica powder is 0.2 or less.
• ⁇ 5> The spherical silica powder according to any one of ⁇ 1> to ⁇ 4>, having a median diameter d50 of 0.5 to 20.0 ⁇ m.
• ⁇ 6> The spherical silica powder according to any one of ⁇ 1> to ⁇ 5>, having a specific surface area of 0.1 to 4.0 m 2 /g. ⁇ 7>
• ⁇ 8> The spherical silica powder according to any one of ⁇ 1> to ⁇ 7>, wherein the spherical silica powder contains 30 to 1500 ppm by mass of Ti.
• a resin composition comprising the spherical silica powder according to any one of ⁇ 1> to ⁇ 8> and a resin.
• Example 1 Silica powder (SO-C2 manufactured by Admatechs Co., Ltd.) was prepared as a silica precursor. 15 g of the silica precursor was washed with 150 ml of distilled water, dried at 200° C. for 12 hours, and then filled into an alumina crucible and heat-treated (fired) at 1200° C. in an air atmosphere for 1 hour. After the heat treatment (fired), the silica precursor was cooled to 25° C. and crushed in an agate mortar to obtain silica powder of Example 1.
• Example 2 The same operation as in Example 1 was carried out except that silica powder produced by a wet method (AGC Si-Tech Co., Ltd.: H-31, d50: 3.5 ⁇ m) was used as the silica precursor, to obtain a silica powder of Example 2.
• Example 3 The same procedure as in Example 2 was carried out except that the silica precursor was calcined under a hydrogen atmosphere, to obtain silica powder of Example 3.
• Example 4 The same procedure as in Example 3 was carried out except that the calcination time of the silica precursor was changed to 3 hours, to obtain silica powder of Example 4.
• Example 5 The same procedure as in Example 2 was carried out except that the silica precursor was calcined under a nitrogen atmosphere containing hydrogen, to obtain silica powder of Example 5. The volume ratio of hydrogen to nitrogen was 1:9.
• silica powder produced by a wet method (AGC Si-Tech Co., Ltd.: H-11, d50: 2.0 ⁇ m) was prepared, and the same operation as in Example 2 was carried out except that the silica precursor was fired in a nitrogen atmosphere containing hydrogen, to obtain silica powder of Example 6.
• the ratio of hydrogen to nitrogen was 1:9 by volume.
• Example 7 As the silica precursor, silica powder produced by a wet method (AGC Si-Tech Co., Ltd.: H-201, d50: 20.0 ⁇ m) was prepared, and the same operation as in Example 2 was carried out except that the silica precursor was fired in a nitrogen atmosphere containing hydrogen, to obtain silica powder of Example 7. The ratio of hydrogen to nitrogen was 1:9 by volume.
• ⁇ Silanol group> The amount of silanol groups on the surface of the spherical silica powder was measured by infrared spectroscopy.
• the infrared spectrum was measured by a diffuse reflectance method using an IR Prestige-21 (manufactured by Shimadzu Corporation) with spherical silica powder dispersed in diamond, in a measurement range of 400 to 4000 cm -1 , a resolution of 4 cm -1 , and an accumulation count of 128.
• the spherical silica powder used was dried in vacuum at 180° C. for 1 hour.
• the IR spectrum was normalized at 800 cm -1 and the baseline was adjusted at 3800 cm -1 .
• the maximum IR peak intensity A within the range of 3600 to 3700 cm -1 , the maximum IR peak intensity B within the range of more than 3700 cm -1 and 3800 cm -1 or less, and the maximum IR peak intensity within the range of 3300 to 3800 cm -1 were determined.
• ⁇ Median diameter> The measurement was performed using a particle size distribution measuring device using a laser diffraction method (MT3300EXII manufactured by Microtrac-Bell). The spherical silica powder was dispersed in the device by irradiating it with ultrasonic waves three times for 60 seconds, and then the measurement was performed. The measurement was performed twice for 60 seconds each, and the average value was calculated.
• the spherical silica powder was dried under reduced pressure at 230° C. to completely remove moisture, and used as a sample.
• the specific surface area of this sample was measured by the multipoint BET method using nitrogen gas with an automatic specific surface area/pore distribution measuring device "Tristar II" manufactured by Micromeritics.
• a dedicated device vector network analyzer E5063A, Keycom Co., Ltd.
• the spherical silica powder was vacuum dried at 150°C, and then the powder was filled into a polytetrafluoroethylene (PTFE) cylinder while being sufficiently tapped, and the dielectric constant of the container was measured, and then the dielectric loss tangent was converted using the filling rate of the powder in the container.
• PTFE polytetrafluoroethylene
• Ti Content> Perchloric acid and hydrofluoric acid were added to the spherical silica powder, and the mixture was ignited to remove the main component silicon. The Ti content was then measured by ICP-AES (inductively coupled plasma atomic emission spectrometry) using an ICPE-9000 (manufactured by Shimadzu Corporation).
• the alumina balls were then removed to obtain a liquid composition.
• the liquid composition was impregnated and coated on a glass cloth conforming to IPC Specification 2116, and heated and dried at 160° C. for 4 minutes to obtain a prepreg.
• Copper foil (thickness: 18 ⁇ m, maximum height roughness Rz: 2 ⁇ m, manufactured by Mitsui Kinzoku Co., Ltd., MT18E) was laminated on both sides of the prepreg, and the resulting product was heat-molded at 230° C. and a pressure of 30 kg/cm 2 for 120 minutes to obtain a resin-coated metal substrate.
• the peel strength between the prepreg and the carrier-coated copper foil was measured in accordance with IPC-TM650-2.4.8.
• the spherical silica powders of Examples 1 and 2, which are comparative examples have a ratio (B/A) of the maximum IR peak intensity A at 3600 to 3700 cm ⁇ 1 originating from internal silanol groups to the maximum IR peak intensity B at more than 3700 cm ⁇ 1 and not more than 3800 cm ⁇ 1 originating from isolated silanol groups on the surface, which is greater than 1.5.
• the dielectric tangent is higher and the peel strength is lower, indicating that the powders have poor adhesion to resin.

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