CN115175873A - Hollow particle, resin composition, and resin molded body and laminate using same - Google Patents

Hollow particle, resin composition, and resin molded body and laminate using same Download PDF

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Publication number
CN115175873A
CN115175873A CN202180016759.7A CN202180016759A CN115175873A CN 115175873 A CN115175873 A CN 115175873A CN 202180016759 A CN202180016759 A CN 202180016759A CN 115175873 A CN115175873 A CN 115175873A
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particles
hollow
resin
resin composition
thickness
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黎氏玉昙
中村司
工藤大辅
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Storas Holding Co
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Kyowa Chemical Industry Co Ltd
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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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to hollow particles, a resin composition, and a resin molded body and a laminate using the resin composition. Provided is a hollow particle which can realize low dielectric constant and light weight while ensuring durability. The hollow particles of the present invention contain silica, have an aspect ratio of 2 or more, and are plate-shaped.

Description

Hollow particle, resin composition, and resin molded body and laminate using same
Technical Field
The present invention relates to hollow particles, a resin composition, and a resin molded body and a laminate using the resin composition.
Background
For example, in recent years, in the field of information communication equipment, electronic components (typically, resin components) are required to have a low dielectric constant and a low dielectric loss tangent in order to cope with communication in a high frequency band. In order to achieve this object, for example, it is proposed to include air having a low relative dielectric constant in the member. Specifically, it has been proposed to introduce air by 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.
On the other hand, it is also required to ensure durability (e.g., mechanical strength such as flexural modulus of elasticity, and dimensional stability) of the member.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2007-56158
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above problems, and an object thereof is to enable reduction in dielectric constant and weight while ensuring durability.
Means for solving the problems
According to one aspect of the present invention, there is provided a hollow particle. The hollow particles contain silica, have an aspect ratio of 2 or more, and are plate-shaped.
In one embodiment, the hollow particles have a major axis of 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 thickness of the shell of the hollow particle is 10nm or more and 100nm or less.
In one embodiment, the hollow particles have a hollow ratio of 20% or more and 95% or less.
According to another aspect of the present invention, there is provided a resin composition. The resin composition comprises a resin and the hollow particles.
According to still another aspect of the present invention, there is provided a resin molded body. The resin molded body is formed from the resin composition.
According to yet another aspect of the present invention, a laminate is provided. The laminate comprises a resin layer formed from the resin composition.
In one embodiment, the thickness of the resin layer is 25 μm or less.
Effects of the invention
According to the present invention, the use of plate-shaped hollow particles can reduce the dielectric constant and weight while securing durability.
Drawings
Fig. 1 is a schematic view illustrating a major diameter and a thickness.
Fig. 2 is a schematic cross-sectional view of a laminate in an embodiment of the present invention.
Fig. 3A is a TEM observation photograph (10000 times) of the hollow particles of example 1.
Fig. 3B is a TEM observation photograph (100000 times) of the hollow particles of example 1.
Fig. 4 is an SEM observation photograph (20000 times) of the core particles used in example 1.
Detailed Description
Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
(definition of terms)
The terms in this specification are defined as follows.
1. Major diameter of the particle
The average value is a value measured by observation with a Scanning Electron Microscope (SEM) or a Transmission Electron Microscope (TEM), and is an average value of the major diameters (for example, L in fig. 1) of the 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. Thickness of the particles
The value is measured by SEM or TEM observation, and is an average value of thicknesses (for example, T in fig. 1) of randomly selected primary particles.
3. Aspect ratio (Long diameter/thickness)
Is a value calculated by dividing the major axis of the particle by the thickness of the particle.
4. Particle size
The particle diameter is an average particle diameter in the particle size distribution measurement.
A. Hollow particles
The hollow particles of one embodiment of the present invention are typically formed of silica. The content of the silica in the hollow particles is, for example, 95 wt% or more, preferably 97 wt% or more, and more preferably 98 wt% or more.
The hollow particles have a plate shape. By adopting the plate shape, the durability, the low dielectric constant, and the weight reduction can be achieved at the same time. In addition, the reduction in size (thickness) of the member to be used can be sufficiently coped with. Further, it is easy to achieve both a high hollow ratio and strength of the hollow particles.
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. Such an aspect ratio provides excellent processability, for example, when a resin composition described later is produced.
The length of the hollow particles is preferably 0.1 μm or more, and more preferably 0.2 μm or more. Such a long diameter can sufficiently satisfy a void ratio described later. On the other hand, the length of the hollow particles is preferably 10 μm or less, and more preferably 5 μm or less. Such a long diameter can contribute to the miniaturization (thin film formation) described above.
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. Such a thickness can sufficiently satisfy a void ratio described later. 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. Such a thickness can contribute to the miniaturization (thinning) described above.
The thickness of the shell of the hollow particle is preferably 10nm or more, and more preferably 15nm or more. Such a thickness can effectively prevent the hollow particles from being broken when, for example, a resin composition described later is produced. On the other hand, the thickness of the shell of the hollow particle is preferably 100nm or less, and more preferably 60nm or less. Such a thickness can sufficiently satisfy a void ratio described later, and can contribute greatly to reduction in dielectric constant and weight. The thickness of the shell can be measured by TEM observation. For example, the thickness of the shell of the randomly selected hollow particles is measured and the average value thereof is calculated.
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. Such a hollow ratio can contribute to, for example, a reduction in dielectric constant and a reduction in weight. On the other hand, the hollow ratio of the hollow particles is preferably 95% or less, and more preferably 90% or less. Such a hollow ratio can effectively prevent the hollow particles from being broken when a resin composition described later is produced, for example. 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 1.5cm 3 A value of 1.0cm or less per gram 3 The ratio of the carbon atoms to the carbon atoms is below g.
The particle diameter of the hollow particles is preferably 0.1 μm or more, and more preferably 0.5 μm or more. On the other hand, the particle diameter of the hollow particles is preferably 10 μm or less, and more preferably 5 μm or less.
The BET specific surface area of the hollow particles may be, for example, 10m 2 A ratio of 30m or more per gram 2 More than g. On the other hand, the BET specific surface area of the hollow particles is preferably 250m 2 A ratio of 200m or less per gram 2 The ratio of the carbon atoms to the carbon atoms is below g.
In one embodiment, the hollow particles are subjected to surface treatment with any appropriate surface treatment agent. As the surface treatment agent, for example, at least 1 selected from the group consisting of higher fatty acids, anionic surfactants, cationic surfactants, phosphate esters, coupling agents, esters of polyhydric alcohols and fatty acids, acrylic polymers, and silicone treatment agents is used.
As the method for producing the hollow particles, any appropriate method can be used. In one embodiment, a method for manufacturing hollow particles includes: coating the core particles with a shell-forming material to obtain core-shell particles; and removing the core particles from the core-shell particles.
As the core particles, any appropriate particles can be used as long as the hollow particles can be produced. Specifically, the shape of the core particle is preferably plate-like. The aspect ratio of the core particle is preferably 2 or more, and more preferably 3 or more. On the other hand, the aspect ratio of the core particle is preferably 100 or less, and more preferably 70 or less.
The long diameter of the core particle is preferably 0.1 μm or more, and more preferably 0.2 μm or more. On the other hand, the long diameter of the core particle is preferably 10 μm or less, and more preferably 5 μm or less. The thickness of the core particle is preferably 0.01 μm or more, and more preferably 0.1 μm or more. On the other hand, the thickness of the core particle is preferably 5 μm or less, and more preferably 2 μm or less.
As the material for forming the core particles, for example, a material that can be dissolved in an acidic solution described later is used. In this case, examples of the material for forming the core particles include hydroxides such as magnesium hydroxide, hydrotalcite, magnesium oxide, and calcium hydroxide, oxides of hydrotalcite, oxides such as zinc oxide and calcium oxide, and carbonate compounds such as calcium carbonate. Among them, magnesium hydroxide and hydrotalcite are preferably used, and magnesium hydroxide is particularly preferably used. This is because, for example, the water can exist stably in an aqueous system. The reason for this is that when the particles are dissolved in an acidic solution described later, no gas (for example, carbon dioxide) is generated, and the occurrence of defects in the obtained hollow particles can be suppressed.
As the shell-forming material, for example, water glass (Na) is used 2 O·nSiO 2 ) Tetraethoxysilane (Si (OCH) 2 CH 3 ) 4 ) Are representative alkoxysilanes.
The amount of coating by the shell-forming material can be adjusted by any suitable method. For example, the coating amount is adjusted by controlling the pH value when the core particles are coated with the shell-forming material containing water glass. Specifically, the water glass can be stable in a high pH region (for example, pH11 or more). Therefore, for example, by lowering the pH (for example, to pH7 or less) using a pH adjuster to condense water glass molecules, silica can be efficiently precipitated on the core particles. As the pH adjustor, an acidic solution is preferably used. Specifically, a solution of a strong acid such as hydrochloric acid, nitric acid, or sulfuric acid, or a solution of a weak acid such as ammonium nitrate or ammonium sulfate is preferably used. The amount of the pH adjuster added is preferably 85% to 98% by neutralization with respect to water glass, for example. If the neutralization rate is too high, not only silica is precipitated on the core particles, but also individual silica particles may be generated. In addition, when the coating is performed with the shell-forming material, the core particles may be dissolved. The shell formation (specifically, the precipitation and formation rate of the shell) can also be promoted by heating (for example, 80 to 90 ℃) when the core particles are covered with the shell-forming material.
The removal of the core particles is typically performed by dissolving the core particles in an acidic solution. As the acidic solution, for example, hydrochloric acid, sulfuric acid, nitric acid are used. The temperature for dissolution is, for example, 30 to 90 ℃ and preferably 50 to 70 ℃. According to such a temperature, the core particles can be efficiently dissolved while suppressing a problem such that the shell is easily broken. In one embodiment, hydrochloric acid is used as the acidic solution, for example, from the viewpoint of recycling a substance (for example, a salt) obtained by reaction with the core particles.
Preferably, the method for producing hollow particles further includes firing the shell (for example, in an atmospheric atmosphere). By firing, for example, the hydrophobicity of the shell (specifically, the silanol group of the shell is changed to siloxane) can be improved, and the dielectric characteristics of the obtained hollow particles can be improved. The firing may be performed at any appropriate timing. It is preferable to remove the core particles from the core-shell particles. The firing temperature is, for example, 300 ℃ to 1300 ℃. The firing time is, for example, 1 to 20 hours.
In one embodiment of the present invention, the hollow particles are used as a function-imparting agent for a resin material. The resin composition containing the hollow particles will be described below.
B. Resin composition
A resin composition according to an embodiment of the present invention includes a resin and the hollow particles.
The resin may be any suitable resin selected according to the intended use of the resin composition to be obtained. For example, the resin may be a thermoplastic resin or a thermosetting resin. Specific examples of the resin include epoxy resins, polyimide resins, polyamide resins, polyamideimide resins, polyether ether ketone resins, polyester resins, polyhydroxy polyether resins, polyolefin resins, fluorine resins, liquid crystal polymers, and modified polyimides. They may be used alone or in combination of 2 or more.
The content ratio of the hollow particles in the resin composition is preferably 0.1 wt% or more, and more preferably 0.5 wt% 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 the hollow particles in an amount of 0.5 parts by weight or more, more preferably 1 part by weight or more, based on 100 parts by weight of the resin. On the other hand, the hollow particles are preferably 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. On the other hand, the volume ratio of the hollow particles in the resin composition is preferably 70% or less, and more preferably 60% or less. This is because, for example, the resin composition has excellent processability.
The resin composition may contain optional components. Examples of the optional components include a curing agent (specifically, a curing agent for the resin), a stress-reducing agent, a coloring agent, an adhesion-improving agent, a mold release agent, a flow-adjusting agent, a defoaming agent, a solvent, and a filler. They may be used alone or in combination of 2 or more. In one embodiment, the resin composition comprises a curing agent. The content of the curing agent is, for example, 1 to 150 parts by weight based on 100 parts by weight of the resin.
As the method for producing the resin composition, any appropriate method can be adopted. Specifically, the hollow particles are dispersed in the resin by any suitable dispersion method to obtain a resin composition. Examples of the dispersion method include dispersion by various mixers such as a homomixer, a disperser, and a ball mill, dispersion by a rotation and revolution mixer, dispersion by a shearing force of a triple roll, and dispersion by ultrasonic treatment.
The resin composition is typically a resin molded article molded into a desired shape. For example, a resin molded body is molded into a desired shape using a mold. In molding the resin molded article, any appropriate treatment (for example, curing treatment) may be applied to the resin composition.
In one embodiment of the present invention, the resin composition is a resin layer contained in a laminate. A laminate having a resin layer formed from the resin composition will be described below.
C. Laminated body
Fig. 2 is a schematic sectional view of a laminate in 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, the in-plane direction of the plate-like hollow particles is preferably oriented in the in-plane direction of the resin layer 11. This is because the resin layer can contribute to thinning. Although not shown, the laminate 10 may include other layers. For example, a substrate (typically a resin film) is laminated on one side of the resin layer 11 (the side on which the metal foil 12 is not disposed). The laminate 10 is typically used as a wired circuit substrate.
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. Such a thickness can sufficiently cope with, for example, recent downsizing of electronic components.
As the metal forming the metal foil, any suitable metal may be used. Examples of such a material include copper, aluminum, nickel, chromium, and gold. They may be used alone, or 2 or more of them may be used in combination. The thickness of the metal foil is, for example, 2 to 35 μm.
As a method for producing the laminate, any appropriate method can be adopted. For example, the resin composition is applied to the substrate 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, thereby obtaining a laminate. Typically, the coating layer is cured by applying a treatment such as heating or light irradiation at an arbitrary appropriate timing. In the coating, the resin composition may be dissolved in any suitable solvent and used.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, the measurement method of each characteristic is as follows.
1. Major diameter of the particle
The long diameter was calculated by SEM observation or TEM observation. Specifically, the major axes of 100 primary particles randomly selected from SEM photographs or TEM photographs of the particles were measured, and the arithmetic mean (average major axis) of the obtained measurement values was obtained. The magnification for SEM observation of the core particles is 20000 times, and the magnification for TEM observation of the hollow particles is 10000 times.
2. Thickness of
The thickness of the particles and the thickness of the shell of the particles 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 measurement values was obtained. Note that the magnification for SEM observation of the core particles was 50000 times, and the magnification for TEM observation 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 is calculated by dividing the average major axis of the particles by the average thickness of the particles.
4. Hollow rate
Calculated from the volume of the nuclear particles and the volume of the hollow particles. Specifically, the value is calculated by (volume per core particle)/(volume per hollow particle) × 100. The volume of each of the core particle and the hollow particle is calculated as follows: the volume of the cylinder is approximated to the actual shape, the major axis is the diameter of the circle, and the thickness is the height of the cylinder.
5. Particle size
The particle diameter (average secondary particle diameter) was measured by a dynamic light scattering method using an Otsuka type "ELSZ-2" (analysis condition is a scattering intensity distribution). The sample for measurement was prepared by adding 0.05g of particles to 70mL of water and then subjecting the mixture to ultrasonic treatment at 300. Mu.A for 3 minutes.
6. Pore volume
"BELsorp-max" from "12510, \\ 124631252112463, \\ 12463125051252305. Specifically, the pore volume was determined by analysis based on the BJH method by measurement using a constant volume gas adsorption method using nitrogen gas.
BET specific surface area
"BELsorp-mini" from "12510, \\ 124631252112463, \\ 12463125051252305. Specifically, the specific surface area was determined by analysis based on the BET multipoint method by measurement using a constant volume gas adsorption method using nitrogen gas.
[ example 1]
The plate-like 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 60g/L with ion-exchanged water to obtain a slurry of magnesium hydroxide.
Subsequently, 6.7L of the resulting magnesium hydroxide slurry was heated to 80 ℃ with stirring, and 0.57mol/L of No. 3 water glass (Na) was added thereto over 10 minutes 2 O·3.14SiO 2 Fuji film and mitsundrug) 268ml. Then, 1340ml of No. 3 water glass and 3.25L of 0.5N hydrochloric acid were further started simultaneously. Here, water glass No. 3 was added over 50 minutes and hydrochloric acid was added over 60 minutes. The slurry thus obtained was aged for 30 minutes, and then dehydrated and washed with water to obtain a cake of the core-shell particle precursor.
Subsequently, the obtained filter cake of the core-shell particle precursor was adjusted to a solid content concentration of 60g/L with ion-exchanged water, and heated to 80 ℃ with stirring, to which 268ml of No. 3 water glass was added in an amount of 0.57mol/L over 10 minutes. Then, 670ml of No. 3 water glass and 1.9L of 0.5N hydrochloric acid were further started simultaneously. Here, water glass No. 3 was added over 25 minutes and hydrochloric acid was added over 35 minutes. The slurry thus obtained was aged for 30 minutes, and then dehydrated and washed to obtain a cake of core-shell particles.
Here, when the obtained core-shell particles were measured by the ATR method using FT-IR (FT/IR-4100 manufactured by JASCO), not only 3500 to 3800cm of magnesium hydroxide was observed -1 The peak from OH in the vicinity was also observed to be 1000 to 1300cm -1 Nearby peaks from Si-O-Si.
Then, 21.6L of 0.7N hydrochloric acid was added to the obtained core-shell particles, and the resulting mixture was resuspended with stirring at room temperature so that the solid content concentration of the core-shell particles became 25g/L, and then the resulting mixture was heated to 60 ℃ and aged for 1 hour to dissolve the core particles, thereby obtaining a slurry of hollow silica.
The obtained hollow silica slurry was dehydrated and washed with water to prepare a hollow silica cake, and the hollow silica cake was dried at 60 ℃ for 28 hours to obtain hollow silica particles (major diameter: 0.86 μm, thickness: 0.26 μm, aspect ratio: 3.3, shell thickness: 30nm, hollow ratio: 66%, particle diameter: 0.95 μm, pore volume: 0.67 cm) 3 (iv)/g, BET specific surface area: 123m 2 /g)。
The hollow silica particles obtained were measured by the ATR method using FT-IR ("FT/IR-4100" manufactured by JASCO), and 3500 to 3800cm of magnesium hydroxide particles was not confirmed -1 Only 1000 to 1300cm of a peak derived from OH in the vicinity was observed -1 Nearby peaks from Si-O-Si. When the hollow silica particles were analyzed by X-ray diffraction ("EMPYRIAN" manufactured by PANalytical), no peak of magnesium hydroxide was observed, and the particles were amorphous silica, and the proportion of silica in the core-shell particles was 26 wt% based on the weight of the hollow silica particles obtained.
[ example 2]
Hollow particles (major axis: 0.88. Mu.m, thickness: 0.28. Mu.m, aspect ratio: 3.1, shell thickness: 40nm, hollow ratio: 59%, particle diameter: 1.20 μm, pore volume: 0.50 cm) were obtained in the same manner as in example 1 except that the hydrochloric acid concentration was changed from 0.5N to 0.52N when forming the core-shell particles 3 (iv)/g, BET specific surface area: 81m 2 /g)。
[ example 3]
Hollow particles (major diameter: 0.246. Mu.m, thickness: 0.116. Mu.m, aspect ratio: 2.1, shell thickness: 23nm, hollow ratio: 53%, particle diameter: 0.94. Mu.m, pore volume: 0.85 cm) were obtained in the same manner as in example 1 except that a plate-like hydrotalcite (DHT 4 available from Kyowa chemical industries Co., ltd.) having a major diameter of 0.2. Mu.m, a thickness of 0.07. Mu.m, and an aspect ratio of 2.9 was used in place of the plate-like magnesium hydroxide particles having a major diameter of 0.8. Mu.m, a thickness of 0.2. Mu.m, and an aspect ratio of 4, and the concentration of hydrochloric acid was set to 0.49N in forming the core-shell particles 3 G, BET specific surface area: 135m 2 /g)。
< TEM Observation >
The observation results of the hollow particles of example 1 by a transmission electron microscope ("JEM-2100 PLUS" manufactured by JEOL Ltd.) are shown in FIG. 3. It was confirmed from FIG. 3 that the particles were plate-like hollow particles having a shell (silica layer) thickness of 30 nm. Fig. 4 shows SEM photographs of magnesium hydroxide particles used as core particles, and fig. 3 and 4 confirm that the core particles are hollow particles having a plate-like shape.
< resin composition >
(1) Mixing by ultrasonic treatment
A resin composition 1 was obtained by mixing 1g of a bisphenol F type epoxy resin ("JER 806" manufactured by Mitsubishi chemical corporation), 0.38g of a curing agent ("LV 11" manufactured by Mitsubishi chemical corporation), and 0.04g of the hollow silica particles obtained in example 1. The mixing was performed by ultrasonic treatment for 1 minute using "NS-200-60" manufactured by Nippon Seiko Seisakusho K.K.K..
(2) Mixing with a homogenizer
A resin composition 2 was obtained by mixing 5g of a bisphenol F type epoxy resin ("JER 806" manufactured by Mitsubishi chemical corporation), 1.9g of a curing agent ("LV 11" manufactured by Mitsubishi chemical corporation), and 0.2g of the hollow silica particles obtained in example 1. Mixing was performed at 8000rpm for 5 minutes using a portable homogenizer (T10\1250512540\124711248363manufacturedby IKA japan.
(3) Mixing using a rotation and revolution mixer
A resin composition 3 was obtained by mixing 5g of a bisphenol F type epoxy resin ("JER 806" manufactured by Mitsubishi chemical corporation), 2.5g of a curing agent ("LV 11" manufactured by Mitsubishi chemical corporation), and 0.875g of the hollow silica particles obtained in example 1. Mixing was carried out at 1700rpm for 3 minutes using a rotation and revolution mixer (manufactured by shiitake chemist corporation, \1245912463, 1257912512540sk-300 SVII).
< resin molded article >
The resin compositions 1 to 3 were poured into silicone resin molds having a thickness of 2mm, respectively, and cured at 80 ℃ for 3 hours to obtain resin molded articles 1 to 3.
The molded body thus obtained was cut with a cross-section polishing machine ("IB-09010 CP" manufactured by JEOL) and the cross-section was observed with SEM ("JSM-7600F" manufactured by JEOL), and as a result, no breakage of the hollow particles was observed in any of the resin molded bodies 1 to 3, and no intrusion of the resin into the hollow particles was observed in any of the resin molded bodies 1 to 3.
Industrial applicability
The hollow particles of the present invention can be suitably used for electronic materials, typically. Further, the present invention can be used for, for example, heat insulating materials, sound insulating materials, impact absorbing materials, stress absorbing materials, optical materials, and lightweight materials.
Description of the reference numerals
L major diameter
T thickness
10. Laminated body
11. Resin layer
12. A metal foil.

Claims (9)

1. A hollow particle comprising silica, having an aspect ratio of 2 or more and being plate-shaped.
2. The hollow particle according to claim 1, wherein the major axis is 0.1 μm or more and 10 μm or less.
3. The hollow particle according to claim 1 or 2, wherein the thickness is 0.01 μm or more and 5 μm or less.
4. The hollow particle according to any one of claims 1 to 3, wherein the thickness of the shell is 10nm or more and 100nm or less.
5. The hollow particle according to any one of claims 1 to 4, wherein a hollow ratio is 20% or more and 95% or less.
6. A resin composition comprising a resin, and the hollow particle according to any one of claims 1 to 5.
7. A resin molded body formed from the resin composition according to claim 6.
8. A laminate having a resin layer formed from the resin composition according to claim 6.
9. The laminate according to claim 8, wherein the thickness of the resin layer is 25 μm or less.
CN202180016759.7A 2020-02-28 2021-01-25 Hollow particle, resin composition, and resin molded body and laminate using same Pending CN115175873A (en)

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