WO2021171858A1 - Hollow particle, resin composition, and resin molded article and laminate each using said resin composition - Google Patents

Hollow particle, resin composition, and resin molded article and laminate each using said resin composition Download PDF

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Publication number
WO2021171858A1
WO2021171858A1 PCT/JP2021/002364 JP2021002364W WO2021171858A1 WO 2021171858 A1 WO2021171858 A1 WO 2021171858A1 JP 2021002364 W JP2021002364 W JP 2021002364W WO 2021171858 A1 WO2021171858 A1 WO 2021171858A1
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Prior art keywords
particles
resin
hollow
resin composition
less
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PCT/JP2021/002364
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French (fr)
Japanese (ja)
Inventor
ティ ノック タン レ
中村　司
大輔 工藤
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協和化学工業株式会社
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Priority to JP2022503168A priority Critical patent/JP7385734B2/en
Priority to KR1020227029228A priority patent/KR20220132584A/en
Priority to CN202180016759.7A priority patent/CN115175873A/en
Publication of WO2021171858A1 publication Critical patent/WO2021171858A1/en

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • 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
    • 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

Definitions

  • the present invention relates to hollow particles, a resin composition, and a resin molded body and a laminated body using the resin composition.
  • the member for example, mechanical strength such as flexural modulus and dimensional stability.
  • the present invention has been made to solve the above problems, and one of the objects of the present invention is to be able to achieve low dielectric constant and light weight while ensuring durability.
  • hollow particles are provided.
  • the hollow particles contain silica and have an aspect ratio of 2 or more and are plate-like.
  • the major axis of the hollow particles is 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the thickness of the hollow particles is 0.01 ⁇ m or more and 5 ⁇ m or less.
  • the shell thickness of the hollow particles is 10 nm or more and 100 nm or less.
  • the hollowness of the hollow particles is 20% or more and 95% or less.
  • a resin composition is provided.
  • This resin composition contains a resin and the above-mentioned hollow particles.
  • a resin molded product is provided.
  • This resin molded body is formed from the above resin composition.
  • a laminate is provided.
  • This laminate has a resin layer formed from the above resin composition.
  • the thickness of the resin layer is 25 ⁇ m or less.
  • FIG. 6 is an SEM observation photograph (20,000 times) of the core particles used in Example 1.
  • Particle major axis A value measured by scanning electron microscope (SEM) or transmission electron microscope (TEM) observation, and is the average value of the major axis (for example, L in FIG. 1) of randomly selected primary particles.
  • the primary particles are the smallest particles observed by SEM or TEM, and are distinguished from aggregated particles (secondary particles).
  • Particle Thickness A value measured by SEM or TEM observation, which is an average value of randomly selected primary particle thicknesses (eg, T in FIG. 1).
  • Aspect ratio (major axis / thickness) It is a value calculated by dividing the thickness of the particles from the major axis of the particles.
  • Particle size The particle size is the average particle size in the particle size distribution measurement.
  • the hollow particles in one embodiment of the present invention are typically formed of silica.
  • the silica content of the hollow particles is, for example, 95% by weight or more, preferably 97% by weight or more, and more preferably 98% by weight or more.
  • the shape of the hollow particles is plate-like.
  • the above-mentioned durability, low dielectric constant, and light weight can be achieved at the same time.
  • the aspect ratio of the hollow particles is 2 or more, preferably 3 or more, and more preferably 4 or more.
  • the aspect ratio of the hollow particles is, for example, 100 or less, preferably 60 or less, and more preferably 50 or less. According to such an aspect ratio, for example, the processability when producing the resin composition described later can be excellent.
  • the major axis of the hollow particles is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more. According to such a major axis, the hollow ratio described later can be sufficiently satisfied. On the other hand, the major axis of the hollow particles is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less. According to such a major axis, it can greatly contribute to the miniaturization (thin film).
  • the thickness of the hollow particles is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and particularly preferably 0.1 ⁇ m or more. With such a thickness, the hollow ratio described later can be sufficiently satisfied. On the other hand, the thickness of the hollow particles is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and particularly preferably 2 ⁇ m or less. With such a thickness, it can greatly contribute to the miniaturization (thin film).
  • the thickness of the shell of the hollow particles is preferably 10 nm or more, more preferably 15 nm or more. According to such a thickness, for example, when the resin composition described later is produced, it is possible to effectively prevent the hollow particles from being broken.
  • the thickness of the shell of the hollow particles is preferably 100 nm or less, more preferably 60 nm or less. With such a thickness, the hollow ratio described later can be sufficiently satisfied, which can greatly contribute to the reduction of the dielectric constant and the weight.
  • the thickness of the shell can be measured by TEM observation. For example, it is obtained by measuring the thickness of the shell of randomly selected hollow particles and calculating the average value thereof.
  • the hollow ratio of the hollow particles is preferably 20% or more, more preferably 30% or more, further preferably 40% or more, and particularly preferably 50% or more. According to such a hollow ratio, for example, it can greatly contribute to lowering the dielectric constant and reducing the weight.
  • the hollow ratio of the hollow particles is preferably 95% or less, more preferably 90% or less. According to such a hollow ratio, for example, when the resin composition described later is produced, it is possible to effectively prevent the hollow particles from being broken.
  • the hollow ratio can be calculated from the volume of the core particles and the volume of the hollow particles, which will be described later.
  • the pore volume of the hollow particles is preferably 1.5 cm 3 / g or less, more preferably 1.0 cm 3 / g or less.
  • the particle size of the hollow particles is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more.
  • the particle size of the hollow particles is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the BET specific surface area of the hollow particles may be, for example, 10 m 2 / g or more, or 30 m 2 / g or more. On the other hand, the BET specific surface area of the hollow particles is preferably 250 m 2 / g or less, more preferably 200 m 2 / g or less.
  • the hollow particles are surface treated with any suitable surface treatment agent.
  • suitable surface treatment agent include higher fatty acids, anionic surfactants, cationic surfactants, phosphoric acid esters, coupling agents, esters of polyhydric alcohols and fatty acids, acrylic polymers and silicone treatment agents. At least one selected from the group consisting of is used.
  • the method of producing hollow particles comprises coating the core particles with a shell-forming material to obtain the core-shell particles, and removing the core particles from the core-shell particles.
  • the core particles any suitable particles can be adopted as long as the hollow particles can be produced.
  • the shape of the core particles is preferably plate-like.
  • the aspect ratio of the core particles is preferably 2 or more, more preferably 3 or more.
  • the aspect ratio of the core particles is preferably 100 or less, more preferably 70 or less.
  • the major axis of the core particles is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more. On the other hand, the major axis of the core particles is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the thickness of the core particles is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more. On the other hand, the thickness of the core particles is preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less.
  • the core particle forming material for example, a material that can be dissolved in an acidic solution described later is used.
  • the material for forming the core particles for example, hydroxides such as magnesium hydroxide, hydrotalcite, magnesium oxide and calcium hydroxide, oxides of hydrotalcite, oxides such as zinc oxide and calcium oxide, and the like. Examples thereof include carbonate compounds such as calcium carbonate.
  • magnesium hydroxide and hydrotalcite are preferably used, and magnesium hydroxide is particularly preferably used. For example, it can exist stably in an aqueous system. Further, when it is dissolved in an acidic solution described later, gas (for example, carbon dioxide gas) is not generated, and it is possible to suppress the occurrence of defects in the obtained hollow particles.
  • gas for example, carbon dioxide gas
  • alkoxysilane typified by water glass (Na 2 O ⁇ nSiO 2 ) and tetraethoxysilane (Si (OCH 2 CH 3 ) 4 ) are used.
  • the amount of coating with the shell-forming material can be adjusted by any suitable method.
  • the coating amount is adjusted by controlling the pH value when coating the core particles with a shell-forming material containing water glass.
  • the water glass can be stable in a high pH region (eg, pH 11 or higher). Therefore, for example, by lowering the pH value with a pH adjuster (for example, to pH 7 or less), water glass molecules can be condensed to efficiently precipitate silica on the core particles.
  • a pH adjuster for example, to pH 7 or less
  • an acidic solution is preferably used.
  • a solution of a strong acid such as hydrochloric acid, nitric acid and sulfuric acid, and a solution of a weak acid such as ammonium nitrate and ammonium sulfate are preferably used.
  • the amount of the pH adjuster added is preferably 85% to 98% in terms of the neutralization rate with respect to water glass, for example. If the neutralization rate is too high, not only silica may be precipitated on the core particles, but also single silica particles may be generated. In addition, there is a risk of dissolving core particles when coating with a shell-forming material. It should be noted that heating (for example, 80 ° C. to 90 ° C.) when coating the core particles with the shell-forming material can also promote shell formation (specifically, shell precipitation and formation rate).
  • the core particles are typically removed by dissolving the core particles in an acidic solution.
  • an acidic solution for example, hydrochloric acid, sulfuric acid, and nitric acid are used.
  • the melting temperature is, for example, 30 ° C. to 90 ° C., preferably 50 ° C. to 70 ° C. With such a temperature, the core particles can be efficiently dissolved while suppressing defects such as the shell becoming fragile.
  • hydrochloric acid is used as the acidic solution from the viewpoint of reusing a substance (for example, a salt) obtained by reacting with core particles.
  • the method for producing hollow particles further comprises firing the shell (eg, in an air atmosphere).
  • firing for example, the hydrophobicity of the shell can be improved (specifically, the silanol group of the shell is changed to siloxane), and the dielectric properties of the obtained hollow particles can be improved.
  • Baking can be performed at any suitable timing. Preferably, it is performed after removing the core particles from the core shell particles.
  • the firing temperature is, for example, 300 ° C to 1300 ° C.
  • the firing time is, for example, 1 hour to 20 hours.
  • the hollow particles are used as a function-imparting agent for a resin material.
  • the resin composition containing the hollow particles will be described.
  • the resin composition in one embodiment of the present invention comprises a resin and the hollow particles described above.
  • the resin for example, any suitable resin can be selected depending on the use of the obtained resin composition and the like.
  • the resin may be a thermoplastic resin or a thermosetting resin.
  • Specific examples of the resin include epoxy resin, polyimide resin, polyamide resin, polyamideimide resin, polyether ether ketone resin, polyester resin, polyhydroxypolyether resin, polyolefin resin, fluororesin, liquid crystal polymer, and modified polyimide. These can be used alone or in combination of two or more.
  • the content ratio of the hollow particles in the resin composition is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more. On the other hand, the content ratio is preferably 90% by weight or less, and more preferably 85% by weight or less.
  • the resin composition preferably contains 0.5 parts by weight or more of hollow particles with respect to 100 parts by weight of the resin, and more preferably 1 part by weight or more.
  • the hollow particles are contained in an amount of 300 parts by weight or less, more preferably 200 parts by weight or less, based on 100 parts by weight of the resin.
  • the volume ratio of the hollow particles in the resin composition is preferably 0.1% or more, and more preferably 0.5% or more.
  • the volume ratio of the hollow particles in the resin composition is preferably 70% or less, more preferably 60% or less. For example, this is because the processability when producing a resin composition can be excellent.
  • the resin composition may contain arbitrary components.
  • Optional components include, for example, a curing agent (specifically, a curing agent for the above resin), a low stress agent, a colorant, an adhesion improver, a mold release agent, a flow conditioner, a defoaming agent, a solvent, and a filler. Can be mentioned. These can be used alone or in combination of two or more.
  • the resin composition comprises a curing agent.
  • the content of the curing agent is, for example, 1 part by weight to 150 parts by weight with respect to 100 parts by weight of the resin.
  • the resin composition is obtained by dispersing the hollow particles in the resin by an arbitrary appropriate dispersion method.
  • the dispersion method include dispersion by various stirrers such as a homomixer, a dispenser, and a ball mill, dispersion by a rotation / revolution mixer, dispersion by a shearing force using three rolls, and dispersion by sonication.
  • the resin composition is typically a resin molded product molded into a desired shape.
  • it is a resin molded body molded into a desired shape using a mold.
  • the resin composition can be subjected to any appropriate treatment (for example, curing treatment).
  • the resin composition is a resin layer contained in a laminate.
  • a laminate having a resin layer formed of the above resin composition will be described.
  • FIG. 2 is a schematic cross-sectional view of the laminated body according to one embodiment of the present invention.
  • the laminate 10 has a resin layer 11 and a metal foil 12.
  • the resin layer 11 is formed from the above resin composition. Specifically, the resin layer 11 contains the resin and the hollow particles. In the resin layer 11, it is preferable that the in-plane direction of the plate-shaped hollow particles is oriented in the in-plane direction of the resin layer 11. This is because it can contribute to thinning the resin layer.
  • the laminate 10 may include other layers. For example, a base material (typically, a resin film) laminated on one side of the resin layer 11 (the side on which the metal foil 12 is not arranged) can be mentioned.
  • the laminate 10 is typically used as a wiring circuit board.
  • the thickness of the resin layer is, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more.
  • the thickness of the resin layer is, for example, 100 ⁇ m or less, preferably 50 ⁇ m or less, and more preferably 25 ⁇ m or less. With such a thickness, for example, it is possible to sufficiently cope with the recent miniaturization of electronic members.
  • metal forming the metal foil Any suitable metal can be used as the metal forming the metal foil.
  • copper, aluminum, nickel, chromium and gold can be mentioned. These can be used alone or in combination of two or more.
  • the thickness of the metal foil is, for example, 2 ⁇ m to 35 ⁇ m.
  • the resin composition is coated on the base material to form a coating layer, and the metal foil is laminated on the coating layer to obtain a laminate.
  • the resin composition is applied to the metal foil to form a coating layer to obtain a laminate.
  • the coating layer is subjected to a treatment such as heating or light irradiation at an arbitrary appropriate timing to cure the coating layer.
  • the above resin composition may be dissolved in any suitable solvent and used.
  • the measurement method for each characteristic is as follows. 1.
  • the major axis was calculated by SEM observation or TEM observation. Specifically, the major axis of 100 primary particles randomly selected from the SEM photograph or the TEM photograph of the particles was measured, and the arithmetic mean (average major axis) of the obtained measured values was obtained.
  • the SEM observation magnification of the core particles was 20000 times, and the TEM observation magnification of the hollow particles was 10000 times.
  • Thickness The particle thickness and the particle shell thickness were calculated by SEM observation or TEM observation.
  • the thicknesses of 100 primary particles randomly selected from SEM photographs or TEM photographs of the particles were measured, and the arithmetic mean (average thickness) of the obtained measured values was obtained.
  • the SEM observation magnification of the core particles was 50,000 times, and the TEM observation magnification of the hollow particles was 10000 times and 10000 times. 3.
  • Aspect ratio The aspect ratio was calculated by SEM observation or TEM observation. Specifically, the aspect ratio was calculated by dividing the average major axis of the particles by the average thickness of the particles. 4.
  • Hollow ratio Calculated from the volume of core particles and the volume of hollow particles. Specifically, it was calculated from (volume per core particle) / (volume per hollow particle) ⁇ 100.
  • the volumes of the core particles and the hollow particles per particle were calculated by approximating the actual shape with the volume of the cylinder, the major axis being the diameter of the circle, and the thickness being the height of the cylinder. 5.
  • Particle size Using "ELSZ-2" manufactured by Otsuka Electronics Co., Ltd., the particle size (average secondary particle size) was measured by a dynamic light scattering method (analysis condition is scattering intensity distribution). The sample for measurement was prepared by adding 0.05 g of particles to 70 mL of water and then sonicating at 300 ⁇ A for 3 minutes. 6. Pore volume Measured by "BELsorp-max" of Microtrac Bell Co., Ltd.
  • the measurement was carried out by a constant-volume gas adsorption method using nitrogen gas, and the pore volume was determined by analysis by the BJH method. 7.
  • BET specific surface area Measured with "BELsorp-mini" of Microtrac Bell Co., Ltd. Specifically, the measurement was carried out by a constant-volume gas adsorption method using nitrogen gas, and the specific surface area was determined by analysis by the BET multipoint method.
  • Example 1 Plate-shaped magnesium hydroxide particles having a major axis of 0.8 ⁇ m, a thickness of 0.2 ⁇ m, and an aspect ratio of 4 were adjusted to a solid content concentration of 60 g / L using ion-exchanged water to obtain a magnesium hydroxide slurry.
  • the cake of the obtained core-shell particle precursor was adjusted to a solid content concentration of 60 g / L with ion-exchanged water and heated to 80 ° C. with stirring, to which 268 ml of No. 3 water glass of 0.57 mol / L was added. Was added over 10 minutes. Then, further, 670 ml of No. 3 water glass and 1.9 L of 0.5 N hydrochloric acid were started to be added at the same time. Here, No. 3 water glass was added over 25 minutes, and hydrochloric acid was added over 35 minutes. The slurry thus obtained was aged for 30 minutes, then dehydrated and washed with water to obtain a cake of core-shell particles.
  • Example 2 Hollow particles (major axis: 0.88 ⁇ m, thickness: 0.28 ⁇ m, aspect ratio: 3. 1. Shell thickness: 40 nm, hollow ratio: 59%, particle size: 1.20 ⁇ m, pore volume: 0.50 cm 3 / g, BET specific surface area: 81 m 2 / g).
  • Example 3 Instead of plate-shaped magnesium hydroxide particles with a major axis of 0.8 ⁇ m, thickness of 0.2 ⁇ m, and an aspect ratio of 4, plate-shaped hydrotalcite with a major axis of 0.2 ⁇ m, thickness of 0.07 ⁇ m, and an aspect ratio of 2.9 (Kyowa Chemical Industry Co., Ltd.) Hollow particles (major axis: major axis:: 0.246 ⁇ m, thickness: 0.116 ⁇ m, aspect ratio: 2.1, shell thickness: 23 nm, hollow ratio: 53%, particle size: 0.94 ⁇ m, pore volume: 0.85 cm 3 / g, BET specific surface area : 135 m 2 / g) was obtained.
  • FIG. 3 shows the observation results of the hollow particles of Example 1 with a transmission electron microscope (“JEM-2100PLUS” manufactured by JEOL Ltd.). From FIG. 3, it was confirmed that the shell (silica layer) was a plate-shaped hollow particle having a thickness of 30 nm.
  • FIG. 4 shows an SEM photograph of the magnesium hydroxide particles used as the core particles, it was confirmed from FIGS. 3 and 4 that the core particles were hollow particles having a plate-like shape.
  • ⁇ Resin composition> (1) Mixing by sonication 1 g of bisphenol F type epoxy resin (“JER806” manufactured by Mitsubishi Chemical Co., Ltd.), 0.38 g of curing agent (“LV11” manufactured by Mitsubishi Chemical Co., Ltd.), and obtained in Example 1. 0.04 g of hollow silica particles were mixed to obtain a resin composition 1. Mixing was carried out by applying ultrasonic treatment with "NS-200-60” manufactured by Nissei Tokyo Office Co., Ltd. for 1 minute. (2) Mixing with a homogenizer 5 g of bisphenol F type epoxy resin (“JER806” manufactured by Mitsubishi Chemical Co., Ltd.), 1.9 g of curing agent (“LV11” manufactured by Mitsubishi Chemical Co., Ltd.) and hollow particles obtained in Example 1.
  • silica particles were mixed to obtain a resin composition 2.
  • Mixing was carried out using a handy homogenizer (“T10 Basic” manufactured by IKA Japan Co., Ltd.) at 8000 rpm for 5 minutes.
  • 0.875 g of hollow grain silica particles were mixed to obtain a resin composition 3.
  • Mixing was carried out using a rotation / revolution mixer (“Kakuhunter SK-300SVII” manufactured by Photochemical Co., Ltd.) at 1700 rpm for 3 minutes.
  • the obtained molded product was cut with a cross section polisher (JEOL's "IB-09010CP"), and the cross section was observed with an SEM (JEOL's "JSM-7600F”).
  • JEOL's "JSM-7600F” SEM
  • no destruction of hollow particles was confirmed.
  • invasion of the resin into the hollow particles was not confirmed in any of the resin molded bodies 1-3.
  • the hollow particles of the present invention can typically be suitably used for electronic materials.
  • it can be used as a heat insulating material, a soundproofing material, a shock-cushioning material, a stress-cushioning material, an optical material, and a weight-reducing material.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

Provided is a hollow particle which can be reduced in electric permittivity and weight while keeping the durability thereof.　The hollow particle according to the present invention contains silica, has an aspect ratio of 2 or more, and has a plate-like shape.

Description

中空粒子、樹脂組成物、ならびに該樹脂組成物を用いた樹脂成形体および積層体Hollow particles, resin composition, and resin molded products and laminates using the resin composition.
　本発明は、中空粒子、樹脂組成物、ならびに該樹脂組成物を用いた樹脂成形体および積層体に関する。 The present invention relates to hollow particles, a resin composition, and a resin molded body and a laminated body using the resin composition.
　例えば、近年、情報通信機器の分野では、高周波数帯での通信に対応すべく、電子部材（代表的には、樹脂部材）の低誘電率化、低誘電正接化が求められている。これを実現すべく、例えば、比誘電率の低い空気を部材に含有させることが提案されている。具体的には、中空粒子を用いて空気を導入することが提案されている（例えば、特許文献１参照）。このように、空気を含有させることで、部材の軽量化にも寄与し得る。 For example, in recent years, in the field of information and communication equipment, in order to support communication in a high frequency band, it is required to reduce the dielectric constant and the low dielectric loss tangent of an electronic member (typically, a resin member). In order to realize this, for example, it has been proposed to include air having a low relative permittivity in the member. Specifically, it has been proposed to introduce air using hollow particles (see, for example, Patent Document 1). By containing air in this way, it is possible to contribute to weight reduction of the member.
　一方で、部材の耐久性（例えば、曲げ弾性率等の機械的強度、寸法安定性）を確保することも求められる。 On the other hand, it is also required to ensure the durability of the member (for example, mechanical strength such as flexural modulus and dimensional stability).
特開２００７－５６１５８号公報JP-A-2007-56158
　本発明は、上記課題を解決するためになされたものであり、耐久性を確保しながら、低誘電率化、軽量化を達成し得ることを目的の１つとする。 The present invention has been made to solve the above problems, and one of the objects of the present invention is to be able to achieve low dielectric constant and light weight while ensuring durability.
　本発明の１つの局面によれば、中空粒子が提供される。この中空粒子は、シリカを含み、アスペクト比が２以上で板状である。
　１つの実施形態においては、上記中空粒子の長径は０．１μｍ以上１０μｍ以下である。
　１つの実施形態においては、上記中空粒子の厚みは０．０１μｍ以上５μｍ以下である。
　１つの実施形態においては、上記中空粒子の殻の厚みは１０ｎｍ以上１００ｎｍ以下である。
　１つの実施形態においては、上記中空粒子の中空率は２０％以上９５％以下である。 According to one aspect of the invention, hollow particles are provided. The hollow particles contain silica and have an aspect ratio of 2 or more and are plate-like.
In one embodiment, the major axis of the hollow particles is 0.1 μm or more and 10 μm or less.
In one embodiment, the thickness of the hollow particles is 0.01 μm or more and 5 μm or less.
In one embodiment, the shell thickness of the hollow particles is 10 nm or more and 100 nm or less.
In one embodiment, the hollowness of the hollow particles is 20% or more and 95% or less.
　本発明の別の局面によれば、樹脂組成物が提供される。この樹脂組成物は、樹脂、および、上記中空粒子を含む。 According to another aspect of the present invention, a resin composition is provided. This resin composition contains a resin and the above-mentioned hollow particles.
　本発明のさらに別の局面によれば、樹脂成形体が提供される。この樹脂成形体は、上記樹脂組成物から形成される。 According to yet another aspect of the present invention, a resin molded product is provided. This resin molded body is formed from the above resin composition.
　本発明のさらに別の局面によれば、積層体が提供される。この積層体は、上記樹脂組成物から形成される樹脂層を有する。
　１つの実施形態においては、上記樹脂層の厚みは２５μｍ以下である。 According to yet another aspect of the present invention, a laminate is provided. This laminate has a resin layer formed from the above resin composition.
In one embodiment, the thickness of the resin layer is 25 μm or less.
　本発明によれば、板状の中空粒子を用いることで、耐久性を確保しながら、低誘電率化、軽量化を達成し得る。 According to the present invention, by using plate-shaped hollow particles, it is possible to achieve low dielectric constant and light weight while ensuring durability.
長径および厚みを説明する模式図である。It is a schematic diagram explaining a major axis and thickness. 本発明の１つの実施形態における積層体の概略断面図である。It is the schematic sectional drawing of the laminated body in one Embodiment of this invention. 実施例１の中空粒子のＴＥＭ観察写真（１００００倍）である。It is a TEM observation photograph (10000 times) of the hollow particle of Example 1. FIG. 実施例１の中空粒子のＴＥＭ観察写真（１０００００倍）である。It is a TEM observation photograph (100,000 times) of the hollow particle of Example 1. FIG. 実施例１で用いたコア粒子のＳＥＭ観察写真（２００００倍）である。6 is an SEM observation photograph (20,000 times) of the core particles used in Example 1.
　以下、本発明の実施形態について説明するが、本発明はこれらの実施形態には限定されない。 Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.
（用語の定義）
　本明細書における用語の定義は、下記の通りである。
１．粒子の長径
　走査型電子顕微鏡（ＳＥＭ）または透過型電子顕微鏡（ＴＥＭ）観察により測定した値であり、無作為に選んだ一次粒子の長径（例えば、図１のＬ）の平均値である。なお、一次粒子とは、ＳＥＭまたはＴＥＭにより観察される最小の粒子であって、凝集している粒子（二次粒子）とは区別される。
２．粒子の厚み
　ＳＥＭまたはＴＥＭ観察により測定した値であり、無作為に選んだ一次粒子の厚み（例えば、図１のＴ）の平均値である。
３．アスペクト比（長径／厚み）
　上記粒子の長径から上記粒子の厚みを除して算出した値である。
４．粒径
　粒径は、粒度分布測定における平均粒径である。 (Definition of terms)
The definitions of terms in the present specification are as follows.
1. 1. Particle major axis A value measured by scanning electron microscope (SEM) or transmission electron microscope (TEM) observation, and is the average value of the major axis (for example, L in FIG. 1) of randomly selected primary particles. The primary particles are the smallest particles observed by SEM or TEM, and are distinguished from aggregated particles (secondary particles).
2. Particle Thickness A value measured by SEM or TEM observation, which is an average value of randomly selected primary particle thicknesses (eg, T in FIG. 1).
3. 3. Aspect ratio (major axis / thickness)
It is a value calculated by dividing the thickness of the particles from the major axis of the particles.
4. Particle size The particle size is the average particle size in the particle size distribution measurement.
Ａ．中空粒子
　本発明の１つの実施形態における中空粒子は、代表的には、シリカで形成される。中空粒子のシリカの含有量は、例えば９５重量％以上であり、好ましくは９７重量％以上、さらに好ましくは９８重量％以上である。 A. Hollow Particles The hollow particles in one embodiment of the present invention are typically formed of silica. The silica content of the hollow particles is, for example, 95% by weight or more, preferably 97% by weight or more, and more preferably 98% by weight or more.
　上記中空粒子の形状は、板状である。板状を採用することにより、上述の耐久性と、低誘電率化、軽量化を同時に達成し得る。また、用いられる部材の小型化（薄膜化）にも十分対応することができる。さらには、高い中空率と中空粒子の強度との両立も図りやすい。 The shape of the hollow particles is plate-like. By adopting the plate shape, the above-mentioned durability, low dielectric constant, and light weight can be achieved at the same time. In addition, it is possible to sufficiently cope with the miniaturization (thin film) of the members used. Furthermore, it is easy to achieve both a high hollow ratio and the strength of hollow particles.
　上記中空粒子のアスペクト比は、２以上であり、好ましくは３以上、さらに好ましくは４以上である。一方、中空粒子のアスペクト比は、例えば１００以下であり、好ましくは６０以下、さらに好ましくは５０以下である。このようなアスペクト比によれば、例えば、後述の樹脂組成物を作製する際の加工性に優れ得る。 The aspect ratio of the hollow particles is 2 or more, preferably 3 or more, and more preferably 4 or more. On the other hand, the aspect ratio of the hollow particles is, for example, 100 or less, preferably 60 or less, and more preferably 50 or less. According to such an aspect ratio, for example, the processability when producing the resin composition described later can be excellent.
　中空粒子の長径は、好ましくは０．１μｍ以上、さらに好ましくは０．２μｍ以上である。このような長径によれば、後述の中空率を十分に満足し得る。一方、中空粒子の長径は、好ましくは１０μｍ以下、さらに好ましくは５μｍ以下である。このような長径によれば、上記小型化（薄膜化）に大きく寄与し得る。 The major axis of the hollow particles is preferably 0.1 μm or more, more preferably 0.2 μm or more. According to such a major axis, the hollow ratio described later can be sufficiently satisfied. On the other hand, the major axis of the hollow particles is preferably 10 μm or less, more preferably 5 μm or less. According to such a major axis, it can greatly contribute to the miniaturization (thin film).
　中空粒子の厚みは、好ましくは０．０１μｍ以上、さらに好ましくは０．０５μｍ以上、特に好ましくは０．１μｍ以上である。このような厚みによれば、後述の中空率を十分に満足し得る。一方、中空粒子の厚みは、好ましくは５μｍ以下、さらに好ましくは３μｍ以下、特に好ましくは２μｍ以下である。このような厚みによれば、上記小型化（薄膜化）に大きく寄与し得る。 The thickness of the hollow particles is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more. With such a thickness, the hollow ratio described later can be sufficiently satisfied. On the other hand, the thickness of the hollow particles is preferably 5 μm or less, more preferably 3 μm or less, and particularly preferably 2 μm or less. With such a thickness, it can greatly contribute to the miniaturization (thin film).
　中空粒子の殻の厚みは、好ましくは１０ｎｍ以上、さらに好ましくは１５ｎｍ以上である。このような厚みによれば、例えば、後述の樹脂組成物を作製する際に、中空粒子が壊れるのを効果的に防止し得る。一方、中空粒子の殻の厚みは、好ましくは１００ｎｍ以下、さらに好ましくは６０ｎｍ以下である。このような厚みによれば、後述の中空率を十分に満足し得、低誘電率化、軽量化に大きく寄与し得る。なお、殻の厚みは、ＴＥＭ観察により測定することができる。例えば、無作為に選んだ中空粒子の殻の厚みを測定し、その平均値を算出することにより求められる。 The thickness of the shell of the hollow particles is preferably 10 nm or more, more preferably 15 nm or more. According to such a thickness, for example, when the resin composition described later is produced, it is possible to effectively prevent the hollow particles from being broken. On the other hand, the thickness of the shell of the hollow particles is preferably 100 nm or less, more preferably 60 nm or less. With such a thickness, the hollow ratio described later can be sufficiently satisfied, which can greatly contribute to the reduction of the dielectric constant and the weight. The thickness of the shell can be measured by TEM observation. For example, it is obtained by measuring the thickness of the shell of randomly selected hollow particles and calculating the average value thereof.
　中空粒子の中空率は、好ましくは２０％以上、より好ましくは３０％以上、さらに好ましくは４０％以上、特に好ましくは５０％以上である。このような中空率によれば、例えば、低誘電率化、軽量化に大きく寄与し得る。一方、中空粒子の中空率は、好ましくは９５％以下、さらに好ましくは９０％以下である。このような中空率によれば、例えば、後述の樹脂組成物を作製する際に、中空粒子が壊れるのを効果的に防止し得る。なお、中空率は、後述のコア粒子の体積と中空粒子の体積から算出することができる。 The hollow ratio of the hollow particles is preferably 20% or more, more preferably 30% or more, further preferably 40% or more, and particularly preferably 50% or more. According to such a hollow ratio, for example, it can greatly contribute to lowering the dielectric constant and reducing the weight. On the other hand, the hollow ratio of the hollow particles is preferably 95% or less, more preferably 90% or less. According to such a hollow ratio, for example, when the resin composition described later is produced, it is possible to effectively prevent the hollow particles from being broken. The hollow ratio can be calculated from the volume of the core particles and the volume of the hollow particles, which will be described later.
　中空粒子の細孔容積は、好ましくは１．５ｃｍ３／ｇ以下、さらに好ましくは１．０ｃｍ３／ｇ以下である。 The pore volume of the hollow particles is preferably 1.5 cm 3 / g or less, more preferably 1.0 cm 3 / g or less.
　中空粒子の粒径は、好ましくは０．１μｍ以上、さらに好ましくは０．５μｍ以上である。一方、中空粒子の粒径は、好ましくは１０μｍ以下、さらに好ましくは５μｍ以下である。 The particle size of the hollow particles is preferably 0.1 μm or more, more preferably 0.5 μm or more. On the other hand, the particle size of the hollow particles is preferably 10 μm or less, more preferably 5 μm or less.
　中空粒子のＢＥＴ比表面積は、例えば１０ｍ２／ｇ以上であってもよく、３０ｍ２／ｇ以上であってもよい。一方、中空粒子のＢＥＴ比表面積は、好ましくは２５０ｍ２／ｇ以下、さらに好ましくは２００ｍ２／ｇ以下である。 The BET specific surface area of the hollow particles may be, for example, 10 m 2 / g or more, or 30 m 2 / g or more. On the other hand, the BET specific surface area of the hollow particles is preferably 250 m 2 / g or less, more preferably 200 m 2 / g or less.
　１つの実施形態においては、上記中空粒子は、任意の適切な表面処理剤による表面処理が施されている。表面処理剤としては、例えば、高級脂肪酸類、アニオン系界面活性剤、カチオン系界面活性剤、リン酸エステル類、カップリング剤、多価アルコールと脂肪酸とのエステル類、アクリル系ポリマーおよびシリコーン処理剤からなる群から選択される少なくとも１つが用いられる。 In one embodiment, the hollow particles are surface treated with any suitable surface treatment agent. Examples of the surface treatment agent include higher fatty acids, anionic surfactants, cationic surfactants, phosphoric acid esters, coupling agents, esters of polyhydric alcohols and fatty acids, acrylic polymers and silicone treatment agents. At least one selected from the group consisting of is used.
　上記中空粒子の製造方法としては、任意の適切な方法が採用され得る。１つの実施形態においては、中空粒子の製造方法は、コア粒子にシェル形成材料を被覆してコアシェル粒子を得ること、および、コアシェル粒子からコア粒子を除去することを含む。 Any appropriate method can be adopted as the method for producing the hollow particles. In one embodiment, the method of producing hollow particles comprises coating the core particles with a shell-forming material to obtain the core-shell particles, and removing the core particles from the core-shell particles.
　上記コア粒子としては、上記中空粒子を製造し得る限り、任意の適切な粒子が採用され得る。具体的には、コア粒子の形状は、板状であることが好ましい。コア粒子のアスペクト比は、好ましくは２以上、さらに好ましくは３以上である。一方、コア粒子のアスペクト比は、好ましくは１００以下であり、さらに好ましくは７０以下である。 As the core particles, any suitable particles can be adopted as long as the hollow particles can be produced. Specifically, the shape of the core particles is preferably plate-like. The aspect ratio of the core particles is preferably 2 or more, more preferably 3 or more. On the other hand, the aspect ratio of the core particles is preferably 100 or less, more preferably 70 or less.
　コア粒子の長径は、好ましくは０．１μｍ以上、さらに好ましくは０．２μｍ以上である。一方、コア粒子の長径は、好ましくは１０μｍ以下、さらに好ましくは５μｍ以下である。コア粒子の厚みは、好ましくは０．０１μｍ以上、さらに好ましくは０．１μｍ以上、である。一方、コア粒子の厚みは、好ましくは５μｍ以下、さらに好ましくは２μｍ以下である。 The major axis of the core particles is preferably 0.1 μm or more, more preferably 0.2 μm or more. On the other hand, the major axis of the core particles is preferably 10 μm or less, more preferably 5 μm or less. The thickness of the core particles is preferably 0.01 μm or more, more preferably 0.1 μm or more. On the other hand, the thickness of the core particles is preferably 5 μm or less, more preferably 2 μm or less.
　コア粒子の形成材料としては、例えば、後述する酸性溶液に溶解し得る材料が用いられる。この場合、コア粒子の形成材料としては、例えば、水酸化マグネシウム、ハイドロタルサイト、酸化マグネシウム、水酸化カルシウム等の水酸化物、ハイドロタルサイトの酸化物、酸化亜鉛、酸化カルシウム等の酸化物、炭酸カルシウム等の炭酸塩化合物が挙げられる。これらの中でも、水酸化マグネシウム、ハイドロタルサイトが好ましく用いられ、水酸化マグネシウムが特に好ましく用いられる。例えば、水系において安定に存在し得るからである。また、後述の酸性溶液に溶解させる際に、ガス（例えば、炭酸ガス）が発生せず、得られる中空粒子に欠陥が生じるのを抑制し得るからである。 As the core particle forming material, for example, a material that can be dissolved in an acidic solution described later is used. In this case, as the material for forming the core particles, for example, hydroxides such as magnesium hydroxide, hydrotalcite, magnesium oxide and calcium hydroxide, oxides of hydrotalcite, oxides such as zinc oxide and calcium oxide, and the like. Examples thereof include carbonate compounds such as calcium carbonate. Among these, magnesium hydroxide and hydrotalcite are preferably used, and magnesium hydroxide is particularly preferably used. For example, it can exist stably in an aqueous system. Further, when it is dissolved in an acidic solution described later, gas (for example, carbon dioxide gas) is not generated, and it is possible to suppress the occurrence of defects in the obtained hollow particles.
　上記シェル形成材料としては、例えば、水ガラス（Ｎａ２Ｏ・ｎＳｉＯ２）、テトラエトキシシラン（Ｓｉ(ＯＣＨ２ＣＨ３）４)に代表されるアルコキシシランが用いられる。 As the shell-forming material, for example, alkoxysilane typified by water glass (Na 2 O · nSiO 2 ) and tetraethoxysilane (Si (OCH 2 CH 3 ) 4 ) are used.
　シェル形成材料による被覆量は、任意の適切な方法により調整され得る。例えば、水ガラスを含むシェル形成材料でコア粒子を被覆する際のｐＨ値を制御することで、被覆量を調整する。具体的には、上記水ガラスは、高ｐＨ領域（例えば、ｐＨ１１以上）において安定であり得る。したがって、例えば、ｐＨ調整剤を用いてｐＨ値を下げることで（例えば、ｐＨ７以下に）、水ガラス分子を縮合させて、シリカを効率的にコア粒子上に析出させ得る。ｐＨ調整剤としては、好ましくは、酸性の溶液が用いられる。具体的には、塩酸、硝酸、硫酸等の強酸の溶液、硝酸アンモニウム、硫酸アンモニウム等の弱酸の溶液が好ましく用いられる。ｐＨ調整剤の添加量は、例えば、水ガラスに対する中和率で８５％～９８％とすることが好ましい。中和率が高すぎると、コア粒子上にシリカが析出するだけでなく、単独のシリカ粒子も生成してしまうおそれがある。また、シェル形成材料による被覆の際に、コア粒子を溶解させるおそれがある。なお、シェル形成材料でコア粒子を被覆する際に加熱（例えば、８０℃～９０℃に）することによっても、シェルの形成（具体的には、シェルの析出および形成速度）を促進し得る。 The amount of coating with the shell-forming material can be adjusted by any suitable method. For example, the coating amount is adjusted by controlling the pH value when coating the core particles with a shell-forming material containing water glass. Specifically, the water glass can be stable in a high pH region (eg, pH 11 or higher). Therefore, for example, by lowering the pH value with a pH adjuster (for example, to pH 7 or less), water glass molecules can be condensed to efficiently precipitate silica on the core particles. As the pH adjuster, an acidic solution is preferably used. Specifically, a solution of a strong acid such as hydrochloric acid, nitric acid and sulfuric acid, and a solution of a weak acid such as ammonium nitrate and ammonium sulfate are preferably used. The amount of the pH adjuster added is preferably 85% to 98% in terms of the neutralization rate with respect to water glass, for example. If the neutralization rate is too high, not only silica may be precipitated on the core particles, but also single silica particles may be generated. In addition, there is a risk of dissolving core particles when coating with a shell-forming material. It should be noted that heating (for example, 80 ° C. to 90 ° C.) when coating the core particles with the shell-forming material can also promote shell formation (specifically, shell precipitation and formation rate).
　上記コア粒子の除去は、代表的には、酸性溶液にコア粒子を溶解させることにより行う。酸性溶液としては、例えば、塩酸、硫酸、硝酸が用いられる。溶解させる温度は、例えば、３０℃～９０℃であり、好ましくは５０℃～７０℃である。このような温度によれば、シェルが壊れやすくなる等の不具合を抑制しながら効率的にコア粒子を溶解させ得る。１つの実施形態においては、例えば、コア粒子と反応して得られる物質（例えば、塩）を再利用する観点から、酸性溶液として塩酸を用いる。 The core particles are typically removed by dissolving the core particles in an acidic solution. As the acidic solution, for example, hydrochloric acid, sulfuric acid, and nitric acid are used. The melting temperature is, for example, 30 ° C. to 90 ° C., preferably 50 ° C. to 70 ° C. With such a temperature, the core particles can be efficiently dissolved while suppressing defects such as the shell becoming fragile. In one embodiment, for example, hydrochloric acid is used as the acidic solution from the viewpoint of reusing a substance (for example, a salt) obtained by reacting with core particles.
　好ましくは、上記中空粒子の製造方法は、シェルを焼成（例えば、大気雰囲気下で）することをさらに含む。焼成を行うことにより、例えば、シェルの疎水性を向上させて（具体的には、シェルのシラノール基をシロキサンに変化させて）、得られる中空粒子の誘電特性を向上させ得る。焼成は、任意の適切なタイミングで行い得る。好ましくは、コアシェル粒子からコア粒子を除去した後に行う。焼成の温度は、例えば、３００℃～１３００℃である。焼成時間は、例えば、１時間～２０時間である。 Preferably, the method for producing hollow particles further comprises firing the shell (eg, in an air atmosphere). By performing firing, for example, the hydrophobicity of the shell can be improved (specifically, the silanol group of the shell is changed to siloxane), and the dielectric properties of the obtained hollow particles can be improved. Baking can be performed at any suitable timing. Preferably, it is performed after removing the core particles from the core shell particles. The firing temperature is, for example, 300 ° C to 1300 ° C. The firing time is, for example, 1 hour to 20 hours.
　本発明の１つの実施形態においては、上記中空粒子は樹脂材料の機能付与剤として用いられる。以下、上記中空粒子を含む樹脂組成物について説明する。 In one embodiment of the present invention, the hollow particles are used as a function-imparting agent for a resin material. Hereinafter, the resin composition containing the hollow particles will be described.
Ｂ．樹脂組成物
　本発明の１つの実施形態における樹脂組成物は、樹脂および上記中空粒子を含む。 B. Resin Composition The resin composition in one embodiment of the present invention comprises a resin and the hollow particles described above.
　上記樹脂は、例えば、得られる樹脂組成物の用途等に応じて、任意の適切な樹脂が選択され得る。例えば、樹脂は熱可塑性樹脂であってもよいし、熱硬化性樹脂であってもよい。樹脂の具体例としては、エポキシ樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリエーテルエーテルケトン樹脂、ポリエステル樹脂、ポリヒドロキシポリエーテル樹脂、ポリオレフィン樹脂、フッ素樹脂、液晶ポリマー、変性ポリイミドが挙げられる。これらは、単独で、または、２種以上を組み合わせて用い得る。 For the above resin, for example, any suitable resin can be selected depending on the use of the obtained resin composition and the like. For example, the resin may be a thermoplastic resin or a thermosetting resin. Specific examples of the resin include epoxy resin, polyimide resin, polyamide resin, polyamideimide resin, polyether ether ketone resin, polyester resin, polyhydroxypolyether resin, polyolefin resin, fluororesin, liquid crystal polymer, and modified polyimide. These can be used alone or in combination of two or more.
　上記樹脂組成物における上記中空粒子の含有割合は、好ましくは０．１重量％以上であり、さらに好ましくは０．５重量％以上である。一方、上記含有割合は、好ましくは９０重量％以下であり、さらに好ましくは８５重量％以下である。 The content ratio of the hollow particles in the resin composition is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more. On the other hand, the content ratio is preferably 90% by weight or less, and more preferably 85% by weight or less.
　樹脂組成物において、樹脂１００重量部に対し、中空粒子を０．５重量部以上含有させることが好ましく、さらに好ましくは１重量部以上である。一方、樹脂１００重量部に対し、中空粒子を３００重量部以下含有させることが好ましく、さらに好ましくは２００重量部以下である。 The resin composition preferably contains 0.5 parts by weight or more of hollow particles with respect to 100 parts by weight of the resin, and more preferably 1 part by weight or more. On the other hand, it is preferable that the hollow particles are contained in an amount of 300 parts by weight or less, more preferably 200 parts by weight or less, based on 100 parts by weight of the resin.
　樹脂組成物における中空粒子の体積比率は、好ましくは０．１％以上であり、さらに好ましくは０．５％以上である。一方、樹脂組成物における中空粒子の体積比率は、好ましくは７０％以下であり、さらに好ましくは６０％以下である。例えば、樹脂組成物を作製する際の加工性に優れ得るからである。 The volume ratio of the hollow particles in the resin composition is preferably 0.1% or more, and more preferably 0.5% or more. On the other hand, the volume ratio of the hollow particles in the resin composition is preferably 70% or less, more preferably 60% or less. For example, this is because the processability when producing a resin composition can be excellent.
　上記樹脂組成物は、任意成分を含み得る。任意成分としては、例えば、硬化剤（具体的には、上記樹脂の硬化剤）、低応力化剤、着色剤、密着向上剤、離型剤、流動調整剤、脱泡剤、溶剤、充填剤が挙げられる。これらは、単独で、または、２種以上を組み合わせて用い得る。１つの実施形態においては、樹脂組成物は硬化剤を含む。硬化剤の含有量は、樹脂１００重量部に対し、例えば、１重量部～１５０重量部である。 The resin composition may contain arbitrary components. Optional components include, for example, a curing agent (specifically, a curing agent for the above resin), a low stress agent, a colorant, an adhesion improver, a mold release agent, a flow conditioner, a defoaming agent, a solvent, and a filler. Can be mentioned. These can be used alone or in combination of two or more. In one embodiment, the resin composition comprises a curing agent. The content of the curing agent is, for example, 1 part by weight to 150 parts by weight with respect to 100 parts by weight of the resin.
　上記樹脂組成物の作製方法としては、任意の適切な方法が採用され得る。具体的には、上記樹脂中に、任意の適切な分散方法により、上記中空粒子を分散させることにより、樹脂組成物を得る。分散方法としては、例えば、ホモミキサー、ディスパー、ボールミル等の各種攪拌機による分散、自転公転ミキサーによる分散、３本ロールを用いた剪断力による分散、超音波処理による分散が挙げられる。 Any appropriate method can be adopted as the method for producing the above resin composition. Specifically, the resin composition is obtained by dispersing the hollow particles in the resin by an arbitrary appropriate dispersion method. Examples of the dispersion method include dispersion by various stirrers such as a homomixer, a dispenser, and a ball mill, dispersion by a rotation / revolution mixer, dispersion by a shearing force using three rolls, and dispersion by sonication.
　上記樹脂組成物は、代表的には、所望の形状に成形された樹脂成形体とされる。例えば、モールドを用いて所望の形状に成形された樹脂成形体とされる。樹脂成形体の成形に際し、樹脂組成物は、任意の適切な処理（例えば、硬化処理）が施され得る。 The resin composition is typically a resin molded product molded into a desired shape. For example, it is a resin molded body molded into a desired shape using a mold. In molding the resin molded product, the resin composition can be subjected to any appropriate treatment (for example, curing treatment).
　本発明の１つの実施形態においては、上記樹脂組成物は、積層体に含まれる樹脂層とされる。以下、上記樹脂組成物で形成される樹脂層を有する積層体について説明する。 In one embodiment of the present invention, the resin composition is a resin layer contained in a laminate. Hereinafter, a laminate having a resin layer formed of the above resin composition will be described.
Ｃ．積層体
　図２は、本発明の１つの実施形態における積層体の概略断面図である。積層体１０は、樹脂層１１と金属箔１２とを有する。樹脂層１１は、上記樹脂組成物から形成される。具体的には、樹脂層１１は、上記樹脂と上記中空粒子とを含む。樹脂層１１において、樹脂層１１の面内方向に、板状の中空粒子の面内方向が配向していることが好ましい。樹脂層の薄膜化に寄与し得るからである。図示しないが、積層体１０は、その他の層を含み得る。例えば、樹脂層１１の片側（金属箔１２が配置されない側）に積層される基材（代表的には、樹脂フィルム）が挙げられる。積層体１０は、代表的には、配線回路基板として用いられる。 C. Laminated Body FIG. 2 is a schematic cross-sectional view of the laminated body according to one embodiment of the present invention. The laminate 10 has a resin layer 11 and a metal foil 12. The resin layer 11 is formed from the above resin composition. Specifically, the resin layer 11 contains the resin and the hollow particles. In the resin layer 11, it is preferable that the in-plane direction of the plate-shaped hollow particles is oriented in the in-plane direction of the resin layer 11. This is because it can contribute to thinning the resin layer. Although not shown, the laminate 10 may include other layers. For example, a base material (typically, a resin film) laminated on one side of the resin layer 11 (the side on which the metal foil 12 is not arranged) can be mentioned. The laminate 10 is typically used as a wiring circuit board.
　上記樹脂層の厚みは、例えば５μｍ以上、好ましくは１０μｍ以上である。一方、樹脂層の厚みは、例えば１００μｍ以下、好ましくは５０μｍ以下、さらに好ましくは２５μｍ以下である。このような厚みによれば、例えば、近年の電子部材の小型化に十分に対応することができる。 The thickness of the resin layer is, for example, 5 μm or more, preferably 10 μm or more. On the other hand, the thickness of the resin layer is, for example, 100 μm or less, preferably 50 μm or less, and more preferably 25 μm or less. With such a thickness, for example, it is possible to sufficiently cope with the recent miniaturization of electronic members.
　上記金属箔を形成する金属としては、任意の適切な金属が用いられ得る。例えば、銅、アルミニウム、ニッケル、クロム、金が挙げられる。これらは、単独で、または、２種以上を組み合わせて用い得る。金属箔の厚みは、例えば、２μｍ～３５μｍである。 Any suitable metal can be used as the metal forming the metal foil. For example, copper, aluminum, nickel, chromium and gold can be mentioned. These can be used alone or in combination of two or more. The thickness of the metal foil is, for example, 2 μm to 35 μm.
　上記積層体の作製方法としては、任意の適切な方法が採用され得る。例えば、上記基材上に上記樹脂組成物を塗工して塗工層を形成し、この塗工層上に上記金属箔を積層して積層体を得る。別の具体例としては、上記金属箔に上記樹脂組成物を塗工して塗工層を形成して積層体を得る。代表的には、任意の適切なタイミングで、塗工層に加熱や光照射等の処理を施し、塗工層を硬化させる。塗工に際し、上記樹脂組成物を、任意の適切な溶剤に溶解させて用いてもよい。 Any appropriate method can be adopted as the method for producing the above-mentioned laminate. For example, the resin composition is coated on the base material to form a coating layer, and the metal foil is laminated on the coating layer to obtain a laminate. As another specific example, the resin composition is applied to the metal foil to form a coating layer to obtain a laminate. Typically, the coating layer is subjected to a treatment such as heating or light irradiation at an arbitrary appropriate timing to cure the coating layer. At the time of coating, the above resin composition may be dissolved in any suitable solvent and used.
　以下、実施例によって本発明を具体的に説明するが、本発明はこれら実施例によって限定されるものではない。なお、各特性の測定方法は、断りがない限り、下記の通りである。
１．粒子の長径
　ＳＥＭ観察またはＴＥＭ観察により長径を算出した。具体的には、粒子のＳＥＭ写真またはＴＥＭ写真の中から無作為に選んだ１００個の一次粒子の長径を測定し、得られた測定値の算術平均（平均長径）を求めた。なお、コア粒子のＳＥＭ観察の倍率は２００００倍、中空粒子のＴＥＭ観察の倍率は１００００倍とした。
２．厚み
　ＳＥＭ観察またはＴＥＭ観察により粒子の厚みおよび粒子の殻の厚みを算出した。具体的には、粒子のＳＥＭ写真またはＴＥＭ写真の中から無作為に選んだ１００個の一次粒子の厚みを測定し、得られた測定値の算術平均（平均厚み）を求めた。なお、コア粒子のＳＥＭ観察の倍率は５００００倍、中空粒子のＴＥＭ観察の倍率は１００００倍および１００００倍とした。
３．アスペクト比
　ＳＥＭ観察またはＴＥＭ観察によりアスペクト比を算出した。具体的には、上記粒子の平均長径を上記粒子の平均厚みで除してアスペクト比を算出した。
４．中空率
　コア粒子の体積と中空粒子の体積から算出した。具体的には、（コア粒子１粒子当たりの体積）／（中空粒子１粒子当たりの体積）×１００から算出した。なお、コア粒子および中空粒子の１粒子当たりの体積は、実際の形状を円柱における体積で近似し、上記長径を円の直径とし、上記厚みを円柱の高さとして算出した。
５．粒径
　大塚電子製の「ＥＬＳＺ－２」を用いて、動的光散乱法により粒径（平均二次粒子径）を測定した（解析条件は散乱強度分布）。測定用試料は、水７０ｍＬに粒子０．０５ｇを加えた後、３００μＡで３分間超音波処理を施すことにより調製した。
６．細孔容積
　マイクロトラック・ベル株式会社の「ＢＥＬｓｏｒｐ－ｍａｘ」で測定した。具体的には、窒素ガスを用いた定容量式ガス吸着法で測定し、ＢＪＨ法による解析で細孔容積を求めた。
７．ＢＥＴ比表面積
　マイクロトラック・ベル株式会社の「ＢＥＬｓｏｒｐ－ｍｉｎｉ」で測定した。具体的には、窒素ガスを用いた定容量式ガス吸着法で測定し、ＢＥＴ多点法による解析で比表面積を求めた。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, the measurement method for each characteristic is as follows.
1. 1. Major axis of particles The major axis was calculated by SEM observation or TEM observation. Specifically, the major axis of 100 primary particles randomly selected from the SEM photograph or the TEM photograph of the particles was measured, and the arithmetic mean (average major axis) of the obtained measured values was obtained. The SEM observation magnification of the core particles was 20000 times, and the TEM observation magnification of the hollow particles was 10000 times.
2. Thickness The particle thickness and the particle shell thickness were calculated by SEM observation or TEM observation. Specifically, the thicknesses of 100 primary particles randomly selected from SEM photographs or TEM photographs of the particles were measured, and the arithmetic mean (average thickness) of the obtained measured values was obtained. The SEM observation magnification of the core particles was 50,000 times, and the TEM observation magnification of the hollow particles was 10000 times and 10000 times.
3. 3. Aspect ratio The aspect ratio was calculated by SEM observation or TEM observation. Specifically, the aspect ratio was calculated by dividing the average major axis of the particles by the average thickness of the particles.
4. Hollow ratio Calculated from the volume of core particles and the volume of hollow particles. Specifically, it was calculated from (volume per core particle) / (volume per hollow particle) × 100. The volumes of the core particles and the hollow particles per particle were calculated by approximating the actual shape with the volume of the cylinder, the major axis being the diameter of the circle, and the thickness being the height of the cylinder.
5. Particle size Using "ELSZ-2" manufactured by Otsuka Electronics Co., Ltd., the particle size (average secondary particle size) was measured by a dynamic light scattering method (analysis condition is scattering intensity distribution). The sample for measurement was prepared by adding 0.05 g of particles to 70 mL of water and then sonicating at 300 μA for 3 minutes.
6. Pore volume Measured by "BELsorp-max" of Microtrac Bell Co., Ltd. Specifically, the measurement was carried out by a constant-volume gas adsorption method using nitrogen gas, and the pore volume was determined by analysis by the BJH method.
7. BET specific surface area Measured with "BELsorp-mini" of Microtrac Bell Co., Ltd. Specifically, the measurement was carried out by a constant-volume gas adsorption method using nitrogen gas, and the specific surface area was determined by analysis by the BET multipoint method.
［実施例１］
　長径０．８μｍ、厚み０．２μｍ、アスペクト比４の板状の水酸化マグネシウム粒子を、イオン交換水を用いて固形分濃度６０ｇ/Ｌに調整し、水酸化マグネシウムのスラリーを得た。 [Example 1]
Plate-shaped magnesium hydroxide particles having a major axis of 0.8 μm, a thickness of 0.2 μm, and an aspect ratio of 4 were adjusted to a solid content concentration of 60 g / L using ion-exchanged water to obtain a magnesium hydroxide slurry.
　次いで、得られた水酸化マグネシウムのスラリー６．７Ｌを撹拌しながら８０℃に加温し、これに、０．５７ｍｏｌ/Ｌの３号水ガラス（Ｎａ２Ｏ・３．１４ＳｉＯ２、富士フィルム和光純薬製）２６８ｍｌを１０分かけて加えた。その後、さらに、３号水ガラス１３４０ｍｌと０．５Ｎの塩酸３．２５Ｌを同時に加え始めた。ここで、３号水ガラスは５０分かけて加え、塩酸は６０分かけて加えた。こうして得られたスラリーを３０分間熟成させた後、脱水・水洗し、コアシェル粒子前駆体のケーキを得た。 Next, 6.7 L of the obtained magnesium hydroxide slurry was heated to 80 ° C. with stirring, and this was mixed with 0.57 mol / L No. 3 water glass (Na 2 O · 3.14SiO 2 , Fujifilm sum). 268 ml (manufactured by Kojunyaku) was added over 10 minutes. After that, 1340 ml of No. 3 water glass and 3.25 L of 0.5 N hydrochloric acid were started to be added at the same time. Here, No. 3 water glass was added over 50 minutes, and hydrochloric acid was added over 60 minutes. The slurry thus obtained was aged for 30 minutes, then dehydrated and washed with water to obtain a cake of core-shell particle precursor.
　次いで、得られたコアシェル粒子前駆体のケーキをイオン交換水で固形分濃度６０ｇ/Ｌに調整し、撹拌しながら８０℃に加温し、これに、０．５７ｍｏｌ/Ｌの３号水ガラス２６８ｍｌを１０分かけて加えた。その後、さらに、３号水ガラス６７０ｍｌと０．５Ｎの塩酸１．９Ｌを同時に加え始めた。ここで、３号水ガラスは２５分かけて加え、塩酸は３５分かけて加えた。こうして得られたスラリーを３０分間熟成させた後、脱水・水洗し、コアシェル粒子のケーキを得た。
　ここで、ＦＴ-ＩＲ（ＪＡＳＣＯ製の「ＦＴ/ＩＲ-４１００」）を用いて得られたコアシェル粒子についてＡＴＲ法で測定したところ、水酸化マグネシウムの３５００～３８００ｃｍ-１付近のＯＨ由来のピークだけでなく、１０００～１３００ｃｍ-１付近のＳｉ－Ｏ－Ｓｉ由来のピークが確認された。 Next, the cake of the obtained core-shell particle precursor was adjusted to a solid content concentration of 60 g / L with ion-exchanged water and heated to 80 ° C. with stirring, to which 268 ml of No. 3 water glass of 0.57 mol / L was added. Was added over 10 minutes. Then, further, 670 ml of No. 3 water glass and 1.9 L of 0.5 N hydrochloric acid were started to be added at the same time. Here, No. 3 water glass was added over 25 minutes, and hydrochloric acid was added over 35 minutes. The slurry thus obtained was aged for 30 minutes, then dehydrated and washed with water to obtain a cake of core-shell particles.
Here, when the core-shell particles obtained by using FT-IR (“FT / IR-4100” manufactured by JASCO) were measured by the ATR method, only the peak derived from OH of magnesium hydroxide near 3500 to 3800 cm-1 was measured. However, a peak derived from Si—O—Si near 1000 to 1300 cm -1 was confirmed.
　次いで、得られたコアシェル粒子に０．７Ｎの塩酸２１．６Ｌを加え、室温撹拌下で再懸濁し、コアシェル粒子の固形分濃度が２５ｇ/Ｌとなるように調整した後、これを６０℃に加温し、１時間熟成させてコア粒子を溶解させ、中空シリカのスラリーを得た。
　得られた中空シリカのスラリーを脱水・水洗して中空シリカのケーキとし、この中空シリカのケーキを６０℃で２８時間乾燥させて中空シリカ粒子（長径：０．８６μｍ、厚み：０．２６μｍ、アスペクト比：３．３、殻の厚み：３０ｎｍ、中空率：６６％、粒径：０．９５μｍ、細孔容積：０．６７ｃｍ３／ｇ、ＢＥＴ比表面積：１２３ｍ２／ｇ）を得た。 Next, 21.6 L of 0.7 N hydrochloric acid was added to the obtained core-shell particles, and the mixture was resuspended under stirring at room temperature to adjust the solid content concentration of the core-shell particles to 25 g / L, and then the temperature was adjusted to 60 ° C. The mixture was heated and aged for 1 hour to dissolve the core particles to obtain a hollow silica slurry.
The obtained hollow silica slurry is dehydrated and washed with water to obtain a hollow silica cake, and the hollow silica cake is dried at 60 ° C. for 28 hours to obtain hollow silica particles (major axis: 0.86 μm, thickness: 0.26 μm, aspect). Ratio: 3.3, shell thickness: 30 nm, hollow ratio: 66%, particle size: 0.95 μm, pore volume: 0.67 cm 3 / g, BET specific surface area: 123 m 2 / g) was obtained.
　ＦＴ-ＩＲ（ＪＡＳＣＯ製の「ＦＴ/ＩＲ-４１００」）を用いて得られた中空シリカ粒子についてＡＴＲ法で測定したところ、水酸化マグネシウム粒子の３５００～３８００ｃｍ-１付近のＯＨ由来のピークは確認されず、１０００～１３００ｃｍ-１付近のＳｉ－Ｏ－Ｓｉ由来のピークのみが確認された。また、Ｘ線回折（ＰＡＮａｌｙｔｉｃａｌ製の「ＥＭＰＹＲＩＡＮ」)で中空シリカ粒子を分析したところ、水酸化マグネシウムのピークは確認されず、アモルファスシリカであった。なお、得られた中空シリカ粒子の重量から、上記コアシェル粒子中のシリカの割合は２６重量％であった。 When the hollow silica particles obtained by using FT-IR (“FT / IR-4100” manufactured by JASCO) were measured by the ATR method, the peak derived from OH of the magnesium hydroxide particles near 3500 to 3800 cm-1 was confirmed. However, only the peak derived from Si—O—Si around 1000 to 1300 cm -1 was confirmed. Moreover, when the hollow silica particles were analyzed by X-ray diffraction (“EMPYRIAN” manufactured by PANalytical), the peak of magnesium hydroxide was not confirmed, and it was amorphous silica. From the weight of the obtained hollow silica particles, the ratio of silica in the core-shell particles was 26% by weight.
［実施例２］
　コアシェル粒子の形成に際し、塩酸の濃度を０．５Ｎから０．５２Ｎにしたこと以外は実施例１と同様にして、中空粒子（長径：０．８８μｍ、厚み：０．２８μｍ、アスペクト比：３．１、殻の厚み：４０ｎｍ、中空率：５９％、粒径：１．２０μｍ、細孔容積：０．５０ｃｍ３／ｇ、ＢＥＴ比表面積：８１ｍ２／ｇ）を得た。 [Example 2]
Hollow particles (major axis: 0.88 μm, thickness: 0.28 μm, aspect ratio: 3. 1. Shell thickness: 40 nm, hollow ratio: 59%, particle size: 1.20 μm, pore volume: 0.50 cm 3 / g, BET specific surface area: 81 m 2 / g).
［実施例３］
　長径０．８μｍ、厚み０．２μｍ、アスペクト比４の板状の水酸化マグネシウム粒子のかわりに長径０．２μｍ、厚み０．０７μｍ、アスペクト比２．９の板状のハイドロタルサイト（協和化学工業株式会社製の「ＤＨＴ４」）を用いたこと、および、コアシェル粒子の形成に際し、塩酸の濃度を０．５Ｎから０．４９Ｎにしたこと以外は実施例１と同様にして、中空粒子（長径：０．２４６μｍ、厚み：０．１１６μｍ、アスペクト比：２．１、殻の厚み：２３ｎｍ、中空率：５３％、粒径：０．９４μｍ、細孔容積：０．８５ｃｍ３／ｇ、ＢＥＴ比表面積：１３５ｍ２／ｇ）を得た。 [Example 3]
Instead of plate-shaped magnesium hydroxide particles with a major axis of 0.8 μm, thickness of 0.2 μm, and an aspect ratio of 4, plate-shaped hydrotalcite with a major axis of 0.2 μm, thickness of 0.07 μm, and an aspect ratio of 2.9 (Kyowa Chemical Industry Co., Ltd.) Hollow particles (major axis: major axis:: 0.246 μm, thickness: 0.116 μm, aspect ratio: 2.1, shell thickness: 23 nm, hollow ratio: 53%, particle size: 0.94 μm, pore volume: 0.85 cm 3 / g, BET specific surface area : 135 m 2 / g) was obtained.
＜ＴＥＭ観察＞
　実施例１の中空粒子について透過型電子顕微鏡（日本電子株式会社製の「ＪＥＭ－２１００ＰＬＵＳ」)による観察結果を図３に示す。図３から、殻（シリカ層）の厚みが３０ｎｍの板状の中空粒子であることが確認された。なお、図４にコア粒子として用いた水酸化マグネシウム粒子のＳＥＭ写真を示すが、図３および図４から、コア粒子の板状形状を保った中空粒子であることが確認された。 <TEM observation>
FIG. 3 shows the observation results of the hollow particles of Example 1 with a transmission electron microscope (“JEM-2100PLUS” manufactured by JEOL Ltd.). From FIG. 3, it was confirmed that the shell (silica layer) was a plate-shaped hollow particle having a thickness of 30 nm. Although FIG. 4 shows an SEM photograph of the magnesium hydroxide particles used as the core particles, it was confirmed from FIGS. 3 and 4 that the core particles were hollow particles having a plate-like shape.
＜樹脂組成物＞
（１）超音波処理による混合
　ビスフェノールＦ型エポキシ樹脂（三菱ケミカル株式会社製の「ＪＥＲ８０６」)１ｇ、硬化剤（三菱ケミカル株式会社製の「ＬＶ１１」）０．３８ｇおよび実施例１で得られた中空粒シリカ粒子０．０４ｇを混合し、樹脂組成物１を得た。混合は、株式会社日本精機製作所製の「ＮＳ-２００-６０」による超音波処理を１分間施すことにより行った。
（２）ホモジナイザーによる混合
　ビスフェノールＦ型エポキシ樹脂（三菱ケミカル株式会社製の「ＪＥＲ８０６」)５ｇ、硬化剤（三菱ケミカル株式会社製の「ＬＶ１１」）１．９ｇおよび実施例１で得られた中空粒シリカ粒子０．２ｇを混合し、樹脂組成物２を得た。混合は、ハンディホモジナイザー（ＩＫＡジャパン株式会社製の「Ｔ１０ベーシック」）を用いて８０００ｒｐｍ、５分の条件で行った。
（３）自転公転ミキサーによる混合
　ビスフェノールＦ型エポキシ樹脂（三菱ケミカル株式会社製の「ＪＥＲ８０６」)５ｇ、硬化剤（三菱ケミカル株式会社製の「ＬＶ１１」）２．５ｇおよび実施例１で得られた中空粒シリカ粒子０．８７５ｇを混合し、樹脂組成物３を得た。混合は、自転公転ミキサー（株式会社写真化学製の「カクハンターＳＫ-３００ＳＶＩＩ」）を用いて１７００ｒｐｍ、３分の条件で行った。 <Resin composition>
(1) Mixing by sonication 1 g of bisphenol F type epoxy resin (“JER806” manufactured by Mitsubishi Chemical Co., Ltd.), 0.38 g of curing agent (“LV11” manufactured by Mitsubishi Chemical Co., Ltd.), and obtained in Example 1. 0.04 g of hollow silica particles were mixed to obtain a resin composition 1. Mixing was carried out by applying ultrasonic treatment with "NS-200-60" manufactured by Nissei Tokyo Office Co., Ltd. for 1 minute.
(2) Mixing with a homogenizer 5 g of bisphenol F type epoxy resin (“JER806” manufactured by Mitsubishi Chemical Co., Ltd.), 1.9 g of curing agent (“LV11” manufactured by Mitsubishi Chemical Co., Ltd.) and hollow particles obtained in Example 1. 0.2 g of silica particles were mixed to obtain a resin composition 2. Mixing was carried out using a handy homogenizer (“T10 Basic” manufactured by IKA Japan Co., Ltd.) at 8000 rpm for 5 minutes.
(3) Mixing with a rotation / revolution mixer 5 g of bisphenol F type epoxy resin (“JER806” manufactured by Mitsubishi Chemical Co., Ltd.), 2.5 g of curing agent (“LV11” manufactured by Mitsubishi Chemical Co., Ltd.), and obtained in Example 1. 0.875 g of hollow grain silica particles were mixed to obtain a resin composition 3. Mixing was carried out using a rotation / revolution mixer (“Kakuhunter SK-300SVII” manufactured by Photochemical Co., Ltd.) at 1700 rpm for 3 minutes.
＜樹脂成形体＞
　上記樹脂組成物１－３を、それぞれ、厚み２ｍｍのシリコーン樹脂製のモールドに流し込み、８０℃で３時間の条件で硬化させて、樹脂成形体１－３を得た。 <Resin molded product>
Each of the above resin compositions 1-3 was poured into a silicone resin mold having a thickness of 2 mm and cured at 80 ° C. for 3 hours to obtain a resin molded product 1-3.
　得られた成形体をクロスセクションポリッシャー（ＪＥＯＬ製の「ＩＢ－０９０１０ＣＰ」）で切断し、断面をＳＥＭ（ＪＥＯＬ製の「ＪＳＭ－７６００Ｆ」)で観察したところ、樹脂成形体１－３のいずれにおいても、中空粒子の破壊は確認されなかった。また、樹脂成形体１－３のいずれにおいても、中空粒子内部への樹脂の侵入は確認されなかった。 The obtained molded product was cut with a cross section polisher (JEOL's "IB-09010CP"), and the cross section was observed with an SEM (JEOL's "JSM-7600F"). However, no destruction of hollow particles was confirmed. In addition, invasion of the resin into the hollow particles was not confirmed in any of the resin molded bodies 1-3.
　本発明の中空粒子は、代表的には、電子材料に好適に用いられ得る。他にも、例えば、断熱材料、防音材料、衝撃緩衝材料、応力緩衝材料、光学材料、軽量化材料に用いられ得る。 The hollow particles of the present invention can typically be suitably used for electronic materials. In addition, for example, it can be used as a heat insulating material, a soundproofing material, a shock-cushioning material, a stress-cushioning material, an optical material, and a weight-reducing material.
　Ｌ　長径
　Ｔ　厚み
１０　積層体
１１　樹脂層
１２　金属箔 L Major axis T Thickness 10 Laminated body 11 Resin layer 12 Metal leaf

Claims (9)

  1. 　シリカを含み、アスペクト比が２以上で板状の中空粒子。 Plate-shaped hollow particles containing silica and having an aspect ratio of 2 or more.
  2. 　長径が０．１μｍ以上１０μｍ以下である、請求項１に記載の中空粒子。 The hollow particle according to claim 1, wherein the major axis is 0.1 μm or more and 10 μm or less.
  3. 　厚みが０．０１μｍ以上５μｍ以下である、請求項１または２に記載の中空粒子。 The hollow particle according to claim 1 or 2, which has a thickness of 0.01 μm or more and 5 μm or less.
  4. 　殻の厚みが１０ｎｍ以上１００ｎｍ以下である、請求項１から３のいずれかに記載の中空粒子。 The hollow particle according to any one of claims 1 to 3, wherein the thickness of the shell is 10 nm or more and 100 nm or less.
  5. 　中空率が２０％以上９５％以下である、請求項１から４のいずれかに記載の中空粒子。 The hollow particle according to any one of claims 1 to 4, wherein the hollow ratio is 20% or more and 95% or less.
  6. 　樹脂、および、
    　請求項１から５のいずれかに記載の中空粒子、
    　を含む、樹脂組成物。     Resin and
    The hollow particle according to any one of claims 1 to 5.
    A resin composition comprising.
  7. 　請求項６に記載の樹脂組成物から形成される、樹脂成形体。 A resin molded product formed from the resin composition according to claim 6.
  8. 　請求項６に記載の樹脂組成物から形成される樹脂層を有する、積層体。 A laminate having a resin layer formed from the resin composition according to claim 6.
  9. 　前記樹脂層の厚みが２５μｍ以下である、請求項８に記載の積層体。 The laminate according to claim 8, wherein the thickness of the resin layer is 25 μm or less.
PCT/JP2021/002364 2020-02-28 2021-01-25 Hollow particle, resin composition, and resin molded article and laminate each using said resin composition WO2021171858A1 (en)

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