WO2023032986A1 - 電子材料用シリカ及びその製造方法 - Google Patents

電子材料用シリカ及びその製造方法 Download PDF

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WO2023032986A1
WO2023032986A1 PCT/JP2022/032603 JP2022032603W WO2023032986A1 WO 2023032986 A1 WO2023032986 A1 WO 2023032986A1 JP 2022032603 W JP2022032603 W JP 2022032603W WO 2023032986 A1 WO2023032986 A1 WO 2023032986A1
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silica
less
treated
peak
treated silica
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PCT/JP2022/032603
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English (en)
French (fr)
Japanese (ja)
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弘樹 谷川
泰之 村上
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堺化学工業株式会社
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Priority to JP2023545605A priority Critical patent/JPWO2023032986A1/ja
Priority to KR1020247007139A priority patent/KR20240054278A/ko
Publication of WO2023032986A1 publication Critical patent/WO2023032986A1/ja

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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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/02—Amorphous 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
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution

Definitions

  • the present invention relates to silica for electronic materials and a method for producing the same.
  • Information communication technology is an indispensable technology in the present age when a large amount of information is exchanged in various fields of society.
  • 5G communication which uses radio waves in a higher frequency band instead of the conventional 4G communication and is capable of communicating a large amount of information
  • Higher frequencies are also being used in electronic devices used for mobile phones.
  • a material with a low dielectric loss tangent is also required for the inorganic filler of resins used in the manufacture of electronic devices, and silica is attracting attention as such a material.
  • Silica used in conventional electronic devices includes fused spherical silica powder after dielectric loss tangent reduction treatment (see Patent Document 1), silica particles with specified particle size distribution, specific surface area and dielectric loss tangent (see Patent Document 2). etc. are disclosed.
  • a method for producing silica used for electronic material applications the steps of preparing a silica particle material by a dry method, first surface-treating the silica particle material with a silane compound having a predetermined functional group, A method for producing a filler for an electronic material comprising a second surface treatment step of surface-treating the treated material particles with a predetermined amount of organosilazane (see Patent Document 3), isolated silanol group content, specific surface area ratio to theoretical surface area is predetermined
  • a method for producing hydrophobic silica particles is disclosed in which an organosilylating agent is reacted with silica, which is a value (see Patent Document 4).
  • An object of the present invention is to provide silica having a low dielectric loss tangent, excellent uniform dispersibility in a resin, and high safety.
  • the present inventors have studied silica, which has a low dielectric loss tangent, is excellent in uniform dispersibility in resin, and has high safety. It was found that isolated hydroxyl groups on the surface of silica, which had been thought to be reduced as much as possible from the point of view, do not significantly affect the loss factor up to a certain amount. Then, we investigated silica that can achieve both good dielectric properties and dispersibility in resin, and found that amorphous silica that satisfies predetermined requirements in FT-IR measurement has good dielectric properties and dispersibility in resin.
  • the surface-treated silica obtained by treating the silica with a surface treatment agent is suitable as an inorganic filler for use in electronic devices that use high-frequency radio waves.
  • amorphous silica has no problem in terms of safety.
  • the present inventors have also found a suitable method for producing surface-treated silica that has such good dielectric properties, is excellent in uniform dispersibility in resins, and has high safety, and has completed the present invention. rice field.
  • the peak intensity ratio (A/B) between the peak A derived from an isolated hydroxyl group and the peak B derived from a hydroxyl group forming a hydrogen bond in FT-IR measurement is 1.0 to 75.0, and , 3500 to 3100 cm ⁇ 1 , a material for producing a filler for an electronic material containing amorphous silica in which there is substantially no peak derived from adsorbed water.
  • the silica has a powder ratio of tan ⁇ to BET specific surface area (tan ⁇ /BET specific surface area) at 1 GHz and 10 GHz, both of which is 1.0 ⁇ 10 -3 or less [1] or [ 2].
  • the silica has a peak intensity ratio (A/B) between a peak A derived from an isolated hydroxyl group and a peak B derived from a hydroxyl group forming a hydrogen bond in FT-IR measurement of 1.0 to 10.0.
  • the material for producing a filler for an electronic material according to any one of [1] to [3], characterized in that:
  • Amorphous surface-treated silica treated with a surface treatment agent wherein the surface-treated silica has a powder tan ⁇ of 1.0 ⁇ 10 -3 or less at 1 GHz and an ⁇ of 3.15.
  • tan ⁇ of the powder at 10 GHz is 3.0 ⁇ 10 -3 or less, ⁇ is 3.15 or less, and the viscosity at 25 ° C. measured under the following conditions is 75000 mPa s or less.
  • Amorphous surface-treated silica characterized by: (conditions) Using the amorphous surface-treated silica and an epoxy resin having a viscosity of 11000 to 15000 mPa s at 25 ° C., the mass ratio of the amorphous surface-treated silica to the epoxy resin (amorphous surface-treated silica: epoxy Resin) is kneaded at a ratio of 4:6 to prepare a resin mixture for affinity evaluation, and the viscosity at 25° C. of the obtained resin mixture for affinity evaluation is measured using a Brookfield viscometer.
  • Amorphous surface-treated silica treated with a surface treatment agent wherein the surface-treated silica has a powder tan ⁇ of 1.0 ⁇ 10 -3 or less at 1 GHz and an ⁇ of 3.15 below, the tan ⁇ of the powder at 10 GHz is 3.0 ⁇ 10 -3 or less, and the ⁇ is 3.15 or less, and a hydrogen bond is formed with the peak A derived from the isolated hydroxyl group in the FT-IR measurement.
  • a resin composition for electronic materials comprising the surface-treated silica according to [5] or [6] and a resin.
  • a method for producing surface-treated silica which comprises a step of firing amorphous silica obtained by a sol-gel method at 600 to 1200 ° C., A step of crushing, if necessary, a step of re-firing the crushed fired silica obtained in the crushing step at 700 to 1200 ° C., and the crushed fired silica obtained in the crushing step or A method for producing surface-treated silica, comprising a step of treating the refired silica obtained in the refired step with a surface treatment agent.
  • the material for producing a filler for an electronic material of the present invention is a highly safe material that can produce surface-treated silica with a low dielectric loss tangent and excellent uniform dispersibility in resin, and uses radio waves in a high frequency band. It can be suitably used as a raw material for inorganic fillers used in electronic devices.
  • FIG. 1 is a diagram showing FT-IR measurement results of refired silica 1 produced in Example 1.
  • FIG. 2 is a diagram showing the FT-IR measurement results of refired silica 2 produced in Example 2.
  • FIG. 4 is a diagram showing the FT-IR measurement results of comparative refired silica 1 produced in Comparative Example 1.
  • FIG. 3 is a diagram showing the FT-IR measurement results of comparative pyrogenic silica 2 produced in Comparative Example 2.
  • FIG. FIG. 2 is a view showing the FT-IR measurement results of refired silica 1 and 2 produced in Examples 1 and 2 and comparative refired silica 1 and comparative calcined silica 2 produced in Comparative Examples 1 and 2, respectively.
  • Materials for producing fillers for electronic materials show, in FT-IR measurement, a peak A derived from an isolated hydroxyl group appearing at 3800 to 3700 cm ⁇ 1 and a hydrogen bond appearing at 3700 to 3600 cm ⁇ 1 .
  • the peak intensity ratio (A/B) with the peak B derived from the formed hydroxyl group is 1.0 to 75.0, and there is substantially no peak derived from adsorbed water at 3500 to 3100 cm -1
  • Non- It is characterized by containing crystalline silica.
  • the present inventor believes that if water is adsorbed to silica, it will adversely affect the dielectric properties, so it is preferable not to have adsorbed water.
  • silica can be sufficiently bonded to the agent. Therefore, by reacting a material containing such silica with a surface treatment agent, a surface-treated silica having a low dielectric loss tangent, excellent uniform dispersibility in resin, and suitable for use as an inorganic filler can be obtained. be able to.
  • amorphous silica free from such problems can be safely handled as a material for surface-treated silica. If the peak intensity ratio (A/B) between the peak A derived from an isolated hydroxyl group in the FT-IR measurement of the silica and the peak B derived from a hydroxyl group forming a hydrogen bond is 1.0 to 75.0 Good, but preferably between 1.0 and 60.0. More preferably, it is 5.0 to 25.0.
  • the silica has substantially no peak derived from adsorbed water at 3500 to 3100 cm -1 in FT-IR measurement, but "substantially does not exist" is detected in peak analysis in FT-IR.
  • the silica forms a hydrogen bond with the peak A derived from an isolated hydroxyl group in the FT-IR measurement of the surface-treated silica obtained by surface-treating the silica with a surface-treating agent of 0.1 to 30% by mass. It is one of preferred embodiments of the present invention that the peak intensity ratio (A/B) to peak B derived from hydroxyl groups is 0.50 or less.
  • the silica of the present invention is used as an inorganic filler after being surface-treated by reacting with a surface treatment agent. A treated silica is obtained.
  • Such surface-treated silica which has few isolated hydroxyl groups on the surface, has a low dielectric loss tangent and excellent uniform dispersibility in resin, and also has excellent moisture resistance because there are few isolated hydroxyl groups that act as water adsorption sites. becomes.
  • Peak A derived from isolated hydroxyl groups in FT-IR measurement of surface-treated silica obtained by surface treatment with a surface treatment agent of 0.1 to 30% by mass with respect to the silica, and derived from hydroxyl groups forming hydrogen bonds
  • the peak intensity ratio (A/B) to peak B is more preferably 0.40 or less. More preferably, it is 0.30 or less.
  • the silica has a peak intensity ratio (A/B) of 1.0 to 10.0 between a peak A derived from an isolated hydroxyl group and a peak B derived from a hydroxyl group forming a hydrogen bond in FT-IR measurement. is one of the preferred embodiments of the present invention.
  • the surface-treated silica having few isolated hydroxyl groups on the surface has a low dielectric loss tangent, excellent uniform dispersibility in resin, and excellent moisture resistance.
  • Silica having a peak intensity ratio (A/B) of 1.0 to 10.0 between peak A derived from an isolated hydroxyl group and peak B derived from a hydroxyl group forming a hydrogen bond in FT-IR measurement has a surface treatment.
  • the peak intensity ratio (A/B) between the peak A derived from an isolated hydroxyl group and the peak B derived from a hydroxyl group forming a hydrogen bond in FT-IR measurement is more preferably 1.0 to 8.0. , more preferably 1.0 to 5.0.
  • the silica preferably has a D50 of 10 ⁇ m or less and a D10/D90 of 0.30 or more in a laser diffraction particle size distribution.
  • the composition obtained by blending the obtained surface-treated silica with a resin is more suitable for forming a thin film.
  • a molded article formed using the composition has a higher surface flatness.
  • D50 of the silica is more preferably 5 ⁇ m or less, and still more preferably 2 ⁇ m or less. Although the lower limit of D50 of silica is not particularly limited, it is usually 0.005 ⁇ m or more.
  • the D10/D90 of the silica is more preferably 0.40 or more, still more preferably 0.60 or more, particularly preferably 0.70 or more, and most preferably 0.75 or more. is.
  • the silica is preferably one having a maximum volume frequency of 15% or more in a laser diffraction particle size distribution.
  • the molded article formed using the composition obtained by blending the obtained surface-treated silica with the resin has a higher surface flatness. Contribute to performance improvement.
  • the maximum volume frequency of the silica is more preferably 20% or more, still more preferably 30% or more, particularly preferably 40% or more, and most preferably 45% or more.
  • silica is obtained by analyzing a total of 100 or more particles in two or more different fields of view in SEM observation using image analysis software Azokun (manufactured by Asahi Kasei Engineering Co., Ltd.), and the maximum possible diameter of each particle Of the (maximum diameter) d, the ratio (dmax/d50) between the maximum particle diameter dmax and the average particle diameter d50 is preferably 5.0 or less.
  • silica having a small particle size and a narrow particle size distribution is preferable as a material for the surface-treated silica.
  • dmax/d50 is more preferably 2.5 or less, and still more preferably 1.8 or less.
  • the lower limit of dmax/d50 is not particularly limited, it is usually 1.01 or more.
  • the average particle diameter d50 obtained from the SEM image is the average value of the particle diameters of 100 or more silica particles automatically extracted from the SEM image by image analysis software.
  • a method for determining the maximum particle size dmax and the average particle size d50 of silica from SEM observation is as described in Examples below.
  • the particle size obtained by laser diffraction particle size distribution is indicated by "D”
  • the particle size obtained by SEM observation is indicated by "d”.
  • the silica preferably has a BET specific surface area of 0.5 m 2 /g or more. With such a specific surface area, the average particle size is relatively small, so it is suitable for thin film applications.
  • the BET specific surface area of the silica is more preferably 1 m 2 /g or more, still more preferably 2 m 2 /g or more.
  • the upper limit of the BET specific surface area of silica is not particularly limited, it is usually 300 m 2 /g or less.
  • the above silica has a ratio of tan ⁇ of powder to BET specific surface area of silica before surface treatment (tan ⁇ /BET specific surface area) at 1 GHz and 10 GHz, both 1.0 ⁇ 10 -3 or less, and ⁇ both 3.15 or less. is preferably
  • An object of the present invention is to provide amorphous surface-treated silica particles having a low dielectric loss tangent and excellent uniform dispersibility in a resin.
  • the peak intensity ratio A / B between the peak A derived from the isolated hydroxyl group on the silica surface and the peak B derived from the hydroxyl group forming a hydrogen bond must be within a predetermined range.
  • the material for producing surface-treated silica particles with low dielectric loss is desired not only to have an appropriate strength ratio A / B, but also to have a low dielectric loss tangent as a characteristic of the silica particles themselves.
  • the isolated hydroxyl groups on the silica surface affect the dielectric properties of silica. Since the amount of isolated hydroxyl groups tends to increase as the specific surface area of silica increases, the dielectric loss tangent value tends to increase as the specific surface area of silica increases.
  • tan ⁇ per unit specific surface area it is possible to evaluate the dielectric properties of the material itself, excluding the influence of the size of the specific surface area.
  • silica having a powder tan ⁇ /BET specific surface area at 1 GHz and 10 GHz of 1.0 ⁇ 10 -3 or less and a dielectric constant ⁇ of both 3.15 or less is used as a material, dielectric properties and resin It is possible to obtain a surface-treated silica excellent in both uniform dispersibility.
  • the value of (tan ⁇ /BET specific surface area) of silica at 1 GHz and 10 GHz is preferably 1.0 ⁇ 10 ⁇ 3 or less. More preferably, it is 9.0 ⁇ 10 ⁇ 4 or less, and still more preferably 5.0 ⁇ 10 ⁇ 4 or less.
  • the lower limit of the value of (tan ⁇ /BET specific surface area) at 1 GHz and 10 GHz is not particularly limited, it is usually 1.0 ⁇ 10 ⁇ 6 or more.
  • the relative dielectric constant ⁇ of the silica powder at 1 GHz and 10 GHz is more preferably 2.9 or less, and still more preferably 2.8 or less.
  • the lower limit of the dielectric constant ⁇ of the powder at 1 GHz is not particularly limited, it is usually 1.0 or more.
  • the value of tan ⁇ and the relative permittivity ⁇ of silica at 1 GHz and 10 GHz can be measured by the methods described in Examples below.
  • the peak intensity ratio (A/B) between the peak A derived from an isolated hydroxyl group and the peak B derived from a hydroxyl group forming a hydrogen bond in FT-IR measurement is 1.0. 0 to 75.0 and as long as it contains amorphous silica with substantially no peak derived from adsorbed water at 3500 to 3100 cm ⁇ 1 , other components may be contained.
  • Other components include metal elements such as Ti, Zr, Zn, Ba, Sr, and Ca, and light elements such as B, C, and N, either singly or as compounds.
  • the ratio of other components contained in the filler-producing material of the electronic material of the present invention is preferably 50% by mass or less with respect to 100% by mass of the filler-producing material of the electronic material. More preferably, it is 20% by mass or less, and still more preferably 10% by mass or less.
  • the silica contained in the material for producing the filler of the electronic material of the present invention has a number of water molecules desorbed at 500° C. to 1000° C. when the temperature is raised from 25° C. to 1000° C. at a rate of 30° C./min. More than 010 mmol/g is preferred. More preferably, it is greater than 0.011 mmol/g.
  • Such silica can be obtained by carrying out the steps up to the surface treatment step in the method for producing surface-treated silica, which will be described later.
  • the surface-treated silica of the present invention has a powder tan ⁇ of 1.0 ⁇ 10 ⁇ 3 or less at 1 GHz, an ⁇ of 3.15 or less, and a powder tan ⁇ of 3.0 ⁇ 10 ⁇ 3 or less at 10 GHz. and an ⁇ of 3.15 or less, and a viscosity of 75000 mPa s or less at 25° C. measured under the following conditions (hereinafter referred to as the first Also referred to as the surface-treated silica of the present invention).
  • amorphous surface-treated silica Using the amorphous surface-treated silica and an epoxy resin having a viscosity of 11000 to 15000 mPa s at 25 ° C., the mass ratio of the amorphous surface-treated silica to the epoxy resin (amorphous surface-treated silica: epoxy Resin) is kneaded at a ratio of 4:6 to prepare a resin mixture for affinity evaluation, and the viscosity at 25° C. of the obtained resin mixture for affinity evaluation is measured using a Brookfield viscometer.
  • Surface-treated silica with such properties has excellent dielectric properties, excellent dispersibility in resins, and high safety, so it can be used as an inorganic filler for electronic devices that use high-frequency radio waves. It can be used preferably.
  • the powder tan ⁇ at 1 GHz of the surface-treated silica of the present invention is more preferably 5.0 ⁇ 10 ⁇ 4 or less, still more preferably 2.0 ⁇ 10 ⁇ 4 or less.
  • the lower limit of tan ⁇ of the powder at 1 GHz is not particularly limited, it is usually 1.0 ⁇ 10 ⁇ 6 or more.
  • the surface-treated silica of the present invention has a powder relative dielectric constant ⁇ at 1 GHz that is more preferably 3.10 or less, and still more preferably 3.00 or less.
  • the lower limit of the dielectric constant ⁇ of the powder at 1 GHz is not particularly limited, it is usually 1.0 or more.
  • the powder tan ⁇ at 10 GHz of the surface-treated silica of the present invention is more preferably 2.0 ⁇ 10 ⁇ 3 or less, still more preferably 1.5 ⁇ 10 ⁇ 3 or less.
  • the lower limit of tan ⁇ of powder at 10 GHz is not particularly limited, it is usually 1.0 ⁇ 10 ⁇ 6 or more.
  • the surface-treated silica of the present invention has a powder dielectric constant ⁇ at 10 GHz, which is more preferably 3.10 or less, and still more preferably 3.00 or less.
  • the lower limit of the dielectric constant ⁇ of the powder at 10 GHz is not particularly limited, it is usually 1.0 or more.
  • the tan ⁇ value and relative dielectric constant ⁇ of the surface-treated silica at 1 GHz and 10 GHz can be measured by the methods described in the examples below.
  • the viscosity of the resin mixture for affinity evaluation obtained by kneading the surface-treated silica of the first invention and the epoxy resin at a mass ratio of 4:6 at 25° C. should be 75000 mPa s or less, but 70000 mPa s or less. is preferably More preferably, it is 60000 mPa ⁇ s or less.
  • the lower limit of the viscosity of the resin mixture for affinity evaluation at 25°C is not particularly limited, it is usually 100 mPa ⁇ s or more.
  • the resin composition for electronic materials containing the surface-treated silica of the present invention and a resin also has a preferable viscosity.
  • An electronic material produced using a substance can also be suitably used as an electronic material.
  • the viscosity of the resin mixture for affinity evaluation at 25° C. can be measured by the method described in Examples below.
  • the present invention also provides an amorphous surface-treated silica treated with a surface treatment agent, wherein the surface-treated silica has a powder tan ⁇ of 1.0 ⁇ 10 ⁇ 3 or less at 1 GHz and an ⁇ of 3 .15 or less, tan ⁇ of the powder at 10 GHz is 3.0 ⁇ 10 -3 or less, and ⁇ is 3.15 or less, and peak A derived from an isolated hydroxyl group in FT-IR measurement forms a hydrogen bond. It is also a surface-treated silica having a peak intensity ratio (A/B) of 0.50 or less to a peak B derived from a hydroxyl group (hereinafter also referred to as the surface-treated silica of the second present invention).
  • A/B peak intensity ratio
  • the peak intensity ratio (A/B) between the peak A derived from an isolated hydroxyl group and the peak B derived from a hydroxyl group forming a hydrogen bond in the FT-IR measurement of the surface-treated silica is preferably 0.40 or less. . It is more preferably 0.30 or less, and still more preferably 0.20 or less.
  • Preferred values of tan ⁇ and ⁇ of the powder at 1 GHz and tan ⁇ and ⁇ of the powder at 10 GHz in the surface-treated silica of the second invention are the same as those of the surface-treated silica of the first invention.
  • the surface-treated silica of the present invention includes the surface-treated silica of the first present invention and the surface-treated silica of the second present invention. is more preferred.
  • the surface-treating agent used for the surface-treated silica of the present invention is not particularly limited as long as it can improve the dispersibility of silica in the resin.
  • One or more of ring agents, silicone oils, organic phosphates and the like can be used.
  • the amount of surface treatment with the surface treatment agent in the surface-treated silica of the present invention is not particularly limited, but it is preferably 0.1 to 30% by mass with respect to 100% by mass of silica before surface treatment. More preferably 0.1 to 20% by mass, still more preferably 0.1 to 10% by mass.
  • the preferred range of the particle diameter, particle size distribution, and BET specific surface area of the surface-treated silica of the present invention is the preferred range of the particle diameter, particle size distribution, and BET specific surface area of the silica contained in the above-described material for producing a filler for electronic materials. Same as range.
  • the proportion of the surface-treated silica of the present invention contained in the resin composition for electronic materials of the present invention is not particularly limited, and may be appropriately selected according to the desired application and properties. is preferably 0.1 to 90% by mass. It is more preferably 1 to 80% by mass, still more preferably 10 to 70% by mass.
  • the resin contained in the resin composition for electronic materials is not particularly limited, and examples thereof include epoxy resin, polyethylene, polypropylene, polyester, polyamide, polyimide, silicone resin, phenol resin, polysulfone, modified polyphenylene ether resin, polyphenylene sulfide resin, and liquid crystal polymer. , fluororesins, etc., and one or more of these can be used.
  • the ratio of the resin contained in the resin composition for electronic materials is not particularly limited, and may be appropriately selected according to the desired application and characteristics. % by mass is preferred. It is more preferably 20 to 99% by mass, still more preferably 30 to 90% by mass.
  • the resin composition for electronic materials may contain a solvent.
  • the solvent is not particularly limited, for example, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; ethers such as dimethyl ether and diethyl ether; , cyclohexylbenzene, dihydrobenzofuran, trimethylbenzene, tetramethylbenzene, etc.; aromatic heterocyclic compounds, such as pyridine, pyrazine, furan, pyrrole, thiophene, methylpyrrolidone; hexane, pentane, heptane , aliphatic hydrocarbon solvents such as cyclohexane; and glycol ethers such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. One or more of these can be used.
  • the content of the solvent in the resin composition for electronic materials is not particularly limited, it is preferably 0 to 50% by weight with respect to 100% by weight of the resin composition for electronic materials. More preferably 0 to 40% by mass, still more preferably 0 to 30% by mass.
  • the resin composition for electronic materials may contain components other than the surface-treated silica, resin, and solvent of the present invention. Other components include fillers, viscosity modifiers, antifoaming agents, and the like.
  • the resin composition for electronic materials may contain one or more other components.
  • the content of the other components is preferably 30% by mass or less with respect to 100% by mass of the resin composition for electronic materials. More preferably, it is 20% by mass or less, and still more preferably 10% by mass or less.
  • the resin composition for electronic materials of the present invention preferably has a viscosity at 25° C. of 100000 mPa ⁇ s or less. Within such a viscosity range, it becomes easier to form a thin film using the resin for electronic materials of the present invention.
  • the viscosity of the resin composition for electronic materials is more preferably 10000 mPa ⁇ s or less, and even more preferably 1000 mPa ⁇ s or less.
  • the viscosity of the resin composition for electronic materials of the present invention can be measured by the same method as the method for measuring the viscosity of the resin mixture for affinity evaluation at 25° C. described in the Examples below.
  • the electronic material of the present invention is produced using the resin composition for electronic materials of the present invention.
  • the resin composition for electronic materials of the present invention may be molded and used in any manner. It is one of the preferred embodiments of the electronic material of the present invention to include a thin film formed from the resin composition for electronic materials, because a thin film having high surface smoothness can be obtained.
  • the present invention is also a method for producing surface-treated silica, comprising a step of firing silica obtained by a sol-gel method at 600 to 1200° C., and A step of crushing the fired silica obtained in the crushing step, if necessary, a step of re-firing the crushed fired silica obtained in the crushing step at 700 to 1200 ° C., and a crushed silica obtained in the crushing step. It is also a method for producing surface-treated silica, comprising a step of surface-treating the fired silica or the re-fired silica obtained in the re-fired step with a surface treatment agent.
  • the fired silica obtained After firing the silica obtained by the sol-gel method at 600 to 1200 ° C., the fired silica obtained is pulverized and, if necessary, re-fired at 700 to 1200 ° C. to obtain the above-mentioned filler of the electronic material of the present invention.
  • the surface-treated silica of the present invention by easily obtaining the silica contained in the production material, and surface-treating the pulverized fired silica or re-fired silica thus obtained with a surface treatment agent. can be done.
  • the step of firing the silica obtained by the sol-gel method at 600 to 1200°C may be performed at 600 to 1200°C, preferably at 700 to 1150°C. More preferably, it is carried out at 800-1100°C.
  • the time for holding at high temperature in the firing step is not particularly limited, but it is preferably 10 to 1500 minutes in consideration of sufficient firing of silica and production efficiency. More preferably 10 to 1000 minutes, still more preferably 30 to 500 minutes.
  • the step of pulverizing the fired silica obtained in the firing step is a step of loosening the aggregates of the primary particles without crushing the primary particles of silica.
  • the step of firing silica obtained by the sol-gel method at 600 to 1200° C. necking due to sintering between silica particles is likely to occur.
  • the particle size of silica can be made uniform and silica with a small variation in particle size distribution can be obtained.
  • the pyrogenic silica pulverized in the pulverization step preferably has a D50 of 10 ⁇ m or less and a D10/D90 of 0.30 or more in a laser diffraction particle size distribution.
  • a composition obtained by blending the surface-treated silica obtained by the method for producing surface-treated silica of the present invention with a resin is obtained.
  • the suitability for thinning becomes more excellent, and a molded article formed using the composition has higher surface flatness.
  • D50 of the silica is more preferably 5 ⁇ m or less, and still more preferably 2 ⁇ m or less.
  • the lower limit of D50 of silica is not particularly limited, it is usually 0.005 ⁇ m or more.
  • the D10/D90 of the silica is more preferably 0.40 or more, still more preferably 0.60 or more, particularly preferably 0.70 or more, and most preferably 0.75 or more. is.
  • the fired silica pulverized in the pulverization step preferably has a maximum volume frequency of 30% or more in a laser diffraction particle size distribution.
  • the molded article formed using the composition obtained by blending the surface-treated silica obtained by the method for producing surface-treated silica of the present invention with a resin has a higher surface flatness. Therefore, it contributes to improving the performance of molded products and electronic materials.
  • the maximum volume frequency of the silica is more preferably 40% or more, still more preferably 45% or more.
  • the fired silica crushed in the above crushing process is obtained by analyzing a total of 100 or more particles in two or more different fields of view in SEM observation using image analysis software Azokun (manufactured by Asahi Kasei Engineering Co., Ltd.).
  • the ratio (dmax/d50) between the maximum particle diameter dmax and the average particle diameter d50 is preferably 5.0 or less.
  • calcined silica with a dmax/d50 of 5.0 or less obtained using a more accurate average particle size (average primary particle size) d50 of calcined silica particles excluding aggregated particles obtained by SEM observation
  • the molded article formed using the composition obtained by blending the surface-treated silica obtained by the method for producing the surface-treated silica of the present invention with a resin has a higher surface flatness, and as a result, the dielectric properties are more uniform. and contributes to improving the performance of electronic materials.
  • dmax/d50 is more preferably 2.5 or less, and still more preferably 1.8 or less. Although the lower limit of dmax/d50 is not particularly limited, it is usually 1.01 or more.
  • the average particle diameter d50 obtained from the SEM image is the average value of the particle diameters of 100 or more silica particles automatically extracted from the SEM image by image analysis software.
  • a method for determining the maximum particle size dmax and the average particle size d50 of silica from SEM observation is as described in Examples below.
  • the fired silica pulverized in the pulverization step preferably has a BET specific surface area of 0.5 m 2 /g or more. With such a specific surface area, the average particle size is relatively small, so it is suitable for thin film applications.
  • the BET specific surface area of the fired silica pulverized in the pulverization step is more preferably 1 m 2 /g or more, and still more preferably 2 m 2 /g or more.
  • the upper limit of the BET specific surface area of silica is not particularly limited, it is usually 300 m 2 /g or less.
  • the step of re-firing the pulverized pyrogenic silica obtained in the pulverizing step at 700 to 1200°C is performed.
  • the particle size of silica can be made uniform and silica with a small variation in particle size distribution can be obtained.
  • pulverization generates a new interface, and the new interface becomes a factor of variation in the amount of hydroxyl groups on the silica surface.
  • the silica after crushing is re-fired in order to control the amount of hydroxyl groups on the surface of the silica after crushing.
  • the obtained silica can be made more excellent in dielectric properties.
  • the method of pulverizing the fired silica obtained in the firing step is not particularly limited as long as the primary particles can be loosened without crushing the primary particles of silica, but it can be performed with an air flow pulverizer or the like.
  • the re-baking process may be performed at 700 to 1200°C, preferably at 800 to 1200°C. It is more preferably carried out at 800 to 1150°C, still more preferably at 850 to 1100°C.
  • the holding time at high temperature during the re-baking step is not particularly limited, but it is preferably 10 to 1500 minutes in consideration of sufficient baking of silica and production efficiency. More preferably 10 to 1000 minutes, still more preferably 30 to 500 minutes.
  • the difference between the calcining temperature and the recalcining temperature is preferably 50° C. or more.
  • the difference between the sintering temperature and the re-sintering temperature is 100° C. or more. More preferably, it is 150° C. or higher.
  • the difference between the firing temperature and the re-firing temperature is usually 600° C. or less.
  • the step of firing or the step of re-firing can be performed at 1050 to 1200 ° C. preferable. Firing or re-firing at such a temperature reduces the number of isolated hydroxyl groups on the surface, resulting in silica in which most of the isolated hydroxyl groups on the surface are consumed by the reaction with the surface treatment agent. Firing at 1050 to 1200°C may be performed in the step of firing or may be performed in the step of refiring, but it is preferable to perform the step of refiring at 1050 to 1200°C.
  • the step of firing the silica obtained by the sol-gel method and the step of re-firing the pulverized fired silica are preferably carried out in a low humidity atmosphere.
  • a low-humidity atmosphere an atmosphere with a humidity of 90% or less at 30° C. before starting the temperature rise is preferable. More preferably, it is an atmosphere with a humidity of 70% or less at 30°C, and even more preferably an atmosphere with a humidity of 60% or less at 30°C.
  • the atmosphere in which the step of firing the silica obtained by the sol-gel method and the step of re-firing the pulverized fired silica are not particularly limited except for a low humidity atmosphere. , an atmosphere of an inert gas such as argon, or the like.
  • the crushing step or the step of recalcining the crushed fired silica and before the step of surface-treating the crushed fired silica or recalcined silica obtained in the crushing step with a surface treatment agent, It is preferable to perform a step of cooling the pulverized fired silica or re-fired silica obtained in the pulverizing step. After cooling, the crushed fired silica or refired silica obtained in the crushing step is subjected to a surface treatment with a surface treatment agent, so that the crushed fired silica or refired silica obtained in the crushing step is processed. and the surface treatment agent can be sufficiently reacted.
  • the crushed fired silica or recalcined silica obtained in the crushing step is preferably cooled to about room temperature, It is preferable to cool the pulverized fired silica or re-fired silica obtained in the pulverizing step at room temperature for 5 to 1000 minutes.
  • the step of surface-treating the crushed fired silica obtained in the crushing step or the refired silica obtained in the refired step with a surface treatment agent it is preferable not to expose it to a humid environment.
  • the crushed pyrogenic silica or recalcined silica obtained in the crushing process comes into contact with a high-humidity environment, isolated hydroxyl groups are generated on the surface of the crushed pyrogenic silica or recalcined silica obtained in the crushing process. , the dielectric loss tangent of the surface-treated silica obtained by performing the surface treatment process may increase.
  • the step of surface-treating the crushed fired silica obtained in the crushing step or the refired silica obtained in the refired step with a surface treatment agent It is preferable to keep the calcined silica in an environment with a humidity of 90% or less at 30°C. More preferably, it is kept in an environment with a humidity of 70% or less at 30°C, and more preferably in an environment with a humidity of 25% or less at 30°C.
  • surface treatment of the crushed calcined silica obtained in the crushing step or the recalcined silica obtained in the recalcining process with a surface treatment agent refers to the surface treatment of the crushed silica obtained in the crushing step. If the crushed fired silica is not re-fired, the crushed fired silica obtained in the crushing step is surface-treated with a surface treatment agent, and if re-fired, the re-fired silica obtained by the re-burning step. It means to surface-treat the refired silica with a surface-treating agent.
  • the proportion of the surface treatment agent used in the surface treatment step is not particularly limited as long as the silica can be surface treated, but the crushed fired silica obtained in the crushing step or the refired silica obtained in the refired step It is preferably 0.1 to 30% by mass with respect to 100% by mass of silica. By using the surface treatment agent in such a ratio, the silica surface can be sufficiently treated and moisture absorption can be prevented.
  • the proportion of the surface treatment agent is more preferably 0.1 to 20% by mass with respect to 100% by mass of the pulverized fired silica or refired silica obtained in the pulverizing step, and more preferably pulverized It is 0.1 to 10% by mass with respect to 100% by mass of pulverized fired silica or refired silica obtained in the process.
  • the surface treatment agent used in the surface treatment step the same agents as those described above can be used.
  • the crushed fired silica or refired silica obtained in the crushing step is sufficiently surface-treated with a surface treatment agent.
  • a surface treatment agent After mixing the pyrogenic silica and the surface treatment agent, it is preferable to heat the mixture to bake the surface treatment agent onto the silica.
  • the heating temperature for the baking treatment may be appropriately set according to the type of the surface treatment agent and the like, but is preferably 30 to 500°C. It is more preferably 50 to 300°C, still more preferably 80 to 250°C.
  • the heating time for the baking treatment is preferably 10 to 600 minutes. More preferably 30 to 400 minutes, still more preferably 60 to 300 minutes.
  • the method for producing surface-treated silica of the present invention may include other steps than the steps described above.
  • Other processes include a dispersion treatment process, a sieving process, a pressurization process, and a crushing process.
  • % and wt% mean “% by weight (% by mass)”.
  • the measuring method of each physical property is as follows. ⁇ FT-IR measurement> Thermo Fisher Scientific K.K. K. A diffuse reflection application was attached to NICOLET 4700 manufactured by Manufacture, and the sample was provided to the measurement jig so that the powder was smooth. Peaks of the obtained data were detected using analysis software OMNIC. Detection of isolated hydroxyl group A: Peak detection was performed after performing auto-baseline correction with an analysis range of 3800 to 3500 cm ⁇ 1 by OMNIC.
  • the threshold value was set to 0.01 for separation from noise, and peaks existing around 3800 to 3700 cm ⁇ 1 were detected. The highest peak intensity was adopted among the peaks.
  • Detection of hydrogen-bonded hydroxyl group B Peak detection was performed after performing auto-baseline correction with an analysis range of 3800 to 3500 cm ⁇ 1 by OMNIC. In peak detection, the threshold value was set to 0.01 for separation from noise, and peaks existing around 3700 to 3600 cm ⁇ 1 were detected. The highest peak intensity was adopted among the peaks.
  • Detection of adsorbed water Peak detection was performed after performing auto-baseline correction with an analysis range of 3500 to 3000 cm ⁇ 1 by OMNIC.
  • the threshold value was set to 0.01 for separation from noise, and the highest peak intensity was adopted among the peaks. Determination of the presence or absence of adsorbed water in the examples means that no peak is detected under the conditions. In both cases, if the detection sensitivity is too high, all noise is detected as a peak, so the sensitivity was adjusted to 5.
  • the measurement range was 2 ⁇ : 20 to 60°, the step width was 0.02°, the counting time was 0.5 s, the voltage was 50 V, and the current was 300 mA.
  • the measurement results were analyzed with analysis software PDXL, and when a peak was detected at 20 to 30° on the software, it was determined that there was crystallinity. A peak search was automatically performed according to the analysis template, and the ⁇ cut value was set to 3.0.
  • ⁇ BET specific surface area> After degassing with a degassing device at a N 2 flow rate of 50 mL/min at 200° C. for 20 min, the specific surface area was measured by the BET 1-point method using Macsorb HM-1220 manufactured by Mountech.
  • Moisture absorption rate (%) ⁇ (ba)/a ⁇ x 100
  • ⁇ Increase rate of dielectric properties and dielectric loss tangent> The dielectric constant ⁇ and the dielectric loss tangent tan ⁇ of the powder at a predetermined frequency were measured using a dielectric constant measuring device manufactured by AET Co., Ltd. using the cavity resonator perturbation method.
  • the dielectric constant ⁇ and the dielectric loss tangent tan ⁇ at 10 GHz of the surface-treated silica after the moisture absorption measurement were measured, and the change in the dielectric loss tangent of the powder before and after the moisture absorption was measured.
  • ⁇ SEM image observation> The silica particles were placed on a sample table and observed with a scanning electron microscope JSM-7000f manufactured by JEOL Ltd. to obtain an SEM image.
  • ⁇ Measurement of maximum particle size dmax and average particle size d50 of silica from images obtained by SEM image observation> The obtained SEM image was analyzed using the image analysis software Azo-kun manufactured by Asahi Kasei Engineering Co., Ltd.
  • the maximum possible diameter d for each of 100 or more particles was randomly analyzed, and the maximum particle diameter dmax and average particle diameter d50 were calculated from the obtained analysis results, and dmax/d50 was calculated.
  • ⁇ Method for preparing resin mixture for affinity evaluation 30.00 g of the surface-treated silica obtained in Examples and Comparative Examples and 45.00 g of an epoxy resin (EPICLON 850 manufactured by DIC Corporation, viscosity at 25° C. of 11000 to 15000 mPa s) were kneaded to prepare a resin mixture for affinity evaluation. made.
  • ⁇ Viscosity measurement> With respect to the obtained resin mixture for affinity evaluation, the viscosity of the resin mixture for affinity evaluation at 25° C. was measured using a Brookfield viscometer model BM manufactured by Tokyo Keiki Co., Ltd.
  • Example 1 Raw material silica synthesized by the sol-gel method was filled in a sagger made of mullite cordierite and placed in a firing furnace. The temperature of the firing furnace was increased at 100°C/h, and the temperature increase was stopped when the temperature reached 1000°C. After sintering at 1000° C. for 5 hours, the temperature was lowered to room temperature at 100° C./h to collect the sintered powder, followed by dry pulverization with an airflow pulverizer. The calcined silica after pulverization was filled in a sagger made of mullite cordierite and placed in a calcining furnace. The temperature of the firing furnace was increased at 100°C/h, and the temperature increase was stopped when the temperature reached 800°C.
  • FIG. 1 shows the FT-IR measurement results of the refired silica 1.
  • Examples 2 and 3 Refired silicas 2 and 3 were obtained in the same manner as in Example 1 except that the refired temperature in the refired step was changed as shown in Table 1, and these were surface-treated to obtain surface-treated silicas 2 and 3.
  • Tables 1 and 2 show the results.
  • FT-IR measurement results of refired silica 2 are shown in FIG.
  • Example 4 Recalcined silica 4 was obtained in the same manner as in Example 1 except that an average particle diameter different from that in Example 1 was used as the raw material silica, and the ratio of HMDS used to the recalcined silica was changed. After treatment, surface-treated silica 4 was obtained. Various measurements similar to those in Example 1 were performed on the obtained refired silica 4 and surface-treated silica 4 . Tables 1 and 2 show the results.
  • Example 5 Recycling was carried out in the same manner as in Example 1, except that an average particle size different from that of Example 1 was used as the raw material silica, the firing and recalcination temperatures were changed, and the ratio of HMDS used to the recalcined silica was changed.
  • a pyrogenic silica 5 was obtained and surface-treated to obtain a surface-treated silica 5.
  • Various measurements similar to those in Example 1 were performed on the obtained refired silica 5 and surface-treated silica 5 . Tables 1 and 2 show the results.
  • Example 6 A recalcined silica 6 was obtained in the same manner as in Example 1. 50.00 g of the obtained recalcined silica 6 was weighed and put into a dry mixer. 0.50 g of a surface treatment agent (phenyltrimethoxysilane (PTMS): KBM-103 manufactured by Shin-Etsu Chemical Co., Ltd.) corresponding to 1.0% by mass with respect to the refired silica 6 was added to the dry mixer and mixed. . After that, the mixed powder was taken out from the dry mixer, put into a dryer, and baked with a surface treatment agent at 150° C. for 3 hours to carry out a surface treatment step, whereby surface-treated silica 6 was obtained. Various measurements similar to those in Example 1 were performed on the obtained refired silica 6 and surface-treated silica 6 . Tables 1 and 2 show the results.
  • a surface treatment agent phenyltrimethoxysilane (PTMS): KBM-103 manufactured by Shin-E
  • Example 7 Using vinyltrimethoxysilane (VTMS: KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.) instead of phenyltrimethoxysilane as a surface treatment agent, using a surface treatment agent equivalent to 0.7% by mass with respect to the refired silica, Refired silica 7 was obtained in the same manner as in Example 6 except that the surface treatment was performed under the baking treatment conditions of the surface treatment agent at 130° C. for 3 hours, and the surface treated silica 7 was obtained by surface treatment.
  • Various measurements similar to those in Example 6 were performed on the obtained refired silica 7 and surface-treated silica 7 . Tables 1 and 2 show the results.
  • Examples 8 and 9 Re-fired silicas 8 and 9 were obtained in the same manner as in Example 1 except that the re-fired temperature in the re-fired step was changed, and these were surface-treated to obtain surface-treated silicas 8 and 9.
  • Various measurements similar to those in Example 1 were performed on the obtained refired silicas 8 and 9 and surface-treated silicas 8 and 9. Tables 1 and 2 show the results.
  • Example 10 Refired silica 10 was obtained in the same manner as in Example 1, except that an average particle diameter different from that of Example 1 was used as raw material silica, and the refired temperature and the ratio of HMDS used to the refired silica were changed. , and surface-treated them to obtain surface-treated silica 10. Various measurements similar to those in Example 1 were performed on the obtained refired silica 10 and surface-treated silica 10 . Tables 1 and 2 show the results.
  • Example 11 Recalcined silica 11 was prepared in the same manner as in Example 1, except that an average particle size different from that in Example 1 was used as the raw material silica, and the recalcination temperature and time, and the ratio of HMDS used to the recalcined silica were changed. and surface-treated them to obtain surface-treated silica 11.
  • Various measurements similar to those in Example 1 were performed on the obtained refired silica 11 and surface-treated silica 11 . Tables 1 and 2 show the results.
  • Example 12 The same as in Example 1, except that the starting silica used had an average particle size different from that of Example 1, the firing temperature was changed, re-firing was not performed, and the ratio of HMDS used to the starting silica was changed. Then, the refired silica 12 was obtained, and the surface treated silica 12 was obtained by surface treatment. Various measurements similar to those in Example 1 were performed on the obtained refired silica 12 and surface-treated silica 12 . Tables 1 and 2 show the results.
  • Example 13 The same as in Example 1, except that an average particle diameter different from that in Example 1 was used as the raw material silica, the firing temperature was changed, and the re-firing temperature and time, and the ratio of HMDS used to the re-firing silica were changed. Then, the refired silica 13 was obtained and surface-treated to obtain the surface-treated silica 13. Various measurements similar to those in Example 1 were performed on the obtained refired silica 13 and surface-treated silica 13 . Tables 1 and 2 show the results.
  • Example 14 Refired silica 14 was obtained in the same manner as in Example 1, except that the average particle size of the raw material silica was different from that of Example 1, and the refired temperature and the ratio of HMDS used to the refired silica were changed. , and surface-treated them to obtain surface-treated silica 14. Various measurements similar to those in Example 1 were performed on the obtained refired silica 14 and surface-treated silica 14 . Tables 1 and 2 show the results.
  • Comparative Examples 1 and 2 Comparative recalcined silica 1 and comparative calcined silica 2 were prepared in the same manner as in Example 1 except that the calcining temperature in the recalcining step was changed to 1300 ° C. (Comparative Example 1) or the recalcining step was not performed (Comparative Example 2). These were surface-treated to obtain comparative surface-treated silicas 1 and 2. Various measurements similar to those in Example 1 were performed on the comparative refired silica 1, the comparative fired silica 2, and the comparative surface-treated silicas 1 and 2 thus obtained. Tables 1 and 2 show the results. In addition, the FT-IR measurement results of comparative recalcined silica 1 and comparative calcined silica 2 are shown in FIGS. FIG. 5 shows the displayed results.
  • Comparative Examples 3 and 4 Competitor's product A (Comparative Example 3) and Competitor's product B (Comparative Example 4) were used as calcined and crushed products of raw material silica, which correspond to the raw material silica subjected to calcining and crushing processes, and recalcined silica Comparative refired silicas 3 and 4 were obtained in the same manner as in Example 1 except that the proportion of HMDS used was changed (Comparative Example 3), and these were surface-treated to obtain comparative surface-treated silicas 3 and 4. rice field.
  • Various measurements similar to those in Example 1 were performed on the obtained comparative refired silicas 3 and 4 and comparative surface-treated silicas 3 and 4. Tables 1 and 2 show the results.
  • Competitor A is crystalline silica having an average particle size of 0.5 ⁇ m produced by a dry method.
  • Competitor B is an amorphous silica produced by the sol-gel method, but peak A derived from an isolated hydroxyl group appearing at 3800 to 3700 cm ⁇ 1 in FT-IR measurement is not observed.
  • Comparative example 5 Same as Example 1, except that a different average particle diameter from that of Example 1 was used as raw material silica, the firing temperature in the re-firing step was changed to 400° C., and the ratio of HMDS used to the re-firing silica was changed. Comparative refired silica 5 was obtained in the same manner and surface treated to obtain comparative surface treated silica 5. Various measurements similar to those in Example 1 were performed on the comparative refired silica 5 and the comparative surface-treated silica 5 thus obtained. Tables 1 and 2 show the results.
  • Comparative example 6 Same as Example 1, except that an average particle size different from that of Example 1 was used as the raw material silica, the firing temperature in the re-firing step was changed to 600°C, and the ratio of HMDS used to the re-firing silica was changed. Comparative refired silica 6 was obtained in the same manner and surface treated to obtain comparative surface treated silica 6. Various measurements similar to those in Example 1 were performed on the comparative refired silica 6 and the comparative surface-treated silica 6 thus obtained. Tables 1 and 2 show the results.
  • the peak intensity ratio (A / B) between the peak A derived from an isolated hydroxyl group and the peak B derived from a hydroxyl group forming a hydrogen bond in the FT-IR measurement. is 1.0 to 75, and there is substantially no peak derived from adsorbed water at 3500 to 3100 cm -1 , and the dielectric loss tangent tan ⁇ per unit specific surface area is low.
  • Surface treatment using amorphous silica as a raw material By doing, it was confirmed that amorphous surface-treated silica excellent in dielectric properties, uniform dispersibility in resin, and viscosity suppression can be obtained.
  • the surface-treated silica of Examples 10 to 14 having a peak intensity ratio (A/B) of 0.50 or less has a lower hygroscopicity and a small change in dielectric properties after being placed in a hygroscopic environment. confirmed.

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JP2007290904A (ja) * 2006-04-25 2007-11-08 Nippon Electric Glass Co Ltd シリカ粒子
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