WO2019017435A1 - Microparticules de composé de silicate et leur méthode de production - Google Patents

Microparticules de composé de silicate et leur méthode de production Download PDF

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WO2019017435A1
WO2019017435A1 PCT/JP2018/027107 JP2018027107W WO2019017435A1 WO 2019017435 A1 WO2019017435 A1 WO 2019017435A1 JP 2018027107 W JP2018027107 W JP 2018027107W WO 2019017435 A1 WO2019017435 A1 WO 2019017435A1
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fine particles
particle diameter
silicate compound
eucryptite
particles
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PCT/JP2018/027107
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English (en)
Japanese (ja)
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加藤　博和
忠之 伊左治
谷本　健二
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日産化学株式会社
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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
    • C01B33/20—Silicates
    • C01B33/22—Magnesium silicates
    • 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
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to silicate compound fine particles and a method of producing the same.
  • the technique which utilizes amorphous silica fine particles as a filler of underfilling is also used. That is, a circuit mounted on a base material by wire bonding, flip chip bonding or the like is likely to be broken by a relatively small force because it is often fragile to external force or stress. Under the circumstances, it has been practiced to infiltrate a liquid curable resin (epoxy resin or the like) called an underfill between substrate parts to secure connection reliability.
  • a liquid curable resin epoxy resin or the like
  • an underfill between substrate parts to secure connection reliability.
  • an inorganic substance having a small CTE amorphous silica A technique of filling fine particles etc. as a filler is used.
  • amorphous silica exhibits a “positive” CTE although it has a small CTE compared to, for example, an epoxy resin.
  • ⁇ -eucryptite ( ⁇ -LiAlSiO 4 ), which is one of silicate compounds, is known as a material having a negative CTE, and it is considered to use it as a filler.
  • ⁇ -eucryptite in order to use ⁇ -eucryptite as a filler for sealing materials and underfilling, it is necessary to reduce the particle size and increase the dispersibility in the resin so that the resin can be filled at a high density.
  • the negative CTE is derived from the specific crystal structure of ⁇ -eucryptite, it is essential to have high crystallinity, particularly in underfilling applications.
  • the epoxy resin or the like may be filled with amorphous silica fine particles for the purpose of reducing the dielectric loss and exhibiting the insulating function.
  • magnesium-containing forsterite (Mg 2 SiO 4 ) or enstatite (MgSiO 3 ), which is one of silicate compounds, is known as a material having a small dielectric loss in a high frequency region and exhibiting high insulation.
  • Mg 2 SiO 4 magnesium-containing forsterite
  • MgSiO 3 enstatite
  • These compounds are used as materials for dielectric ceramics used in the microwave region, but to be used as a filler to reduce the dielectric loss of the resin, as in the case of ⁇ -eucryptite, the resin
  • Patent Document 1 describes that heat treatment at 1000 to 1400 ° C. is preferable when synthesizing single phase eucryptite.
  • a solution containing a water-soluble magnesium salt and colloidal silica is spray-dried and then fired at a temperature of 800 to 1000 ° C. in the air, so that the primary particle diameter by electron microscope observation is 1 without passing through the pulverizing step.
  • a method of producing forsterite fine particles in the range of ⁇ 200 nm is disclosed (see, for example, Patent Document 5).
  • Patent Document 3 since the obtained ⁇ -eucryptite is not excellent in crushing property and crushing property, when making the particle diameter smaller, it has to be crushed with strong energy. Similar to the above-mentioned Patent Document 1, when such pulverization is carried out, the particle shape is in the form of rectangular particles having irregular sizes and shapes, so that the dispersibility in the resin is lowered, and the filling amount is excessively limited. .
  • Patent Document 5 since the heat treatment causes strong fusion between particles, sufficient dispersibility in the resin can not be obtained. In order to improve the dispersibility, it is conceivable to reduce the particle size by wet pulverization or the like. However, similar to Patent Document 4, by undergoing such pulverization, the reduction of crystallinity and the formation of an amorphous phase occur, and the dielectric In some cases, the effect of reducing the loss can not be obtained sufficiently.
  • the present invention has been made in view of such circumstances, and it is an object of the present invention to provide silicate compound fine particles having a small particle diameter, excellent dispersibility in a resin, and high crystallinity, and a method for producing the same. .
  • the present inventors have crushed a silicate compound as a raw material to a particle diameter within a predetermined range, and then grind the finely divided particles at a relatively low temperature. It has been found that by firing in a temperature range, it is possible to produce silicate compound fine particles having a small particle size, excellent in dispersibility in a resin, and high crystallinity.
  • the present invention relates to fine particles of a silicate compound as described in any one of the following first to fourth aspects and a method for producing the same.
  • the ratio (d 50 / d S ) of the primary particle diameter (d S ) converted to spherical particles from the specific surface area by nitrogen adsorption method and the dispersed particle diameter (d 50 ) is 1.0 or more It is less than 3.0, and the crystallite diameter calculated from the X-ray diffraction peak belonging to the (102) plane of the ⁇ -eucryptite phase is 45 nm or more and 100 nm or less. .
  • the specific surface area measured by the nitrogen adsorption method and the primary particle diameter in terms of spherical particles (d S), and the dispersion particle diameter (d 50), of (the ratio d 50 / d S) is 1.0 or more It is less than 3.0, and the crystallite diameter calculated from the X-ray diffraction peak belonging to the (112) plane of the forsterite phase is 30 nm or more and 100 nm or less.
  • step (B) a step of firing at a temperature of 750 ° C. or more and less than 950 ° C. which is a method of producing fine particles of a silicate compound.
  • the method further comprises the step (C) of dispersing the fired fine particles such that the dispersed particle diameter (d 50 ) is in the range of 0.1 ⁇ m to 2.0 ⁇ m. It is a manufacturing method of the silicate compound fine particles as described in three viewpoints.
  • silicate compound fine particles having a small particle size, excellent dispersibility in a resin, and high crystallinity.
  • Such fine particles of the silicate compound of the present invention can be suitably used as a filler for semiconductor sealing materials and underfilling.
  • Electron microscope image of silicate compound particles according to Examples 1 and 2 Electron microscope image of fine particles of silicate compound according to Examples 3 and 4 Electron microscope image of silicate compound particles according to Comparative Examples 1 and 4
  • silicate compound fine particles according to the present invention and the method for producing the same will be described.
  • the following description shows one aspect of the present invention, and can be arbitrarily changed within the scope of the present invention.
  • the present invention relates to silicate compound fine particles and a method of producing the same.
  • the silicate compound is, for example, a compound used as a filler for a semiconductor sealing material or underfilling, and examples thereof include ⁇ -eucryptite and forsterite. Therefore, the modes for carrying out the present invention will be described in detail by dividing the case where the silicate compound is ⁇ -eucryptite and the case where it is forsterite.
  • Silicate compound ( ⁇ -eucryptite) fine particles are dispersed in primary particle diameter d S converted to spherical particles from specific surface area by nitrogen adsorption method, and dispersed A crystal calculated from an X-ray diffraction peak belonging to the (102) plane of the ⁇ -eucryptite phase which has a ratio (d 50 / d S ) of the particle diameter d 50 of 1.0 to less than 3.0.
  • the diameter is 45 nm or more and 100 nm or less.
  • Such ⁇ -eucryptite microparticles can be produced through a process including specific (A) steps and (B) steps. That is, in the step (A), the silicate compound as the raw material is pulverized to a small particle size (for example, the dispersed particle size d 50 is 0.1 ⁇ m or more and 2.0 ⁇ m or less). In the subsequent step (B), the fine particles pulverized in the previous step (A) are fired in a specific temperature range.
  • the temperature range in the step (B) is lower than the temperature range such as "sintering" in which a sintered body is obtained by sintering an aggregate of fine particles.
  • a sintering process for obtaining a sintered body of pulverized particles is often performed after the process of pulverizing the raw material.
  • a temperature range lower than the temperature for such sintering is set. Then, in relation to the temperature range in the step (B), it is determined in the above-mentioned step (A) whether or not the raw material is crushed to any particle size.
  • step (B) since sintering is performed in a specific temperature range lower than conventional sintering, it is possible to avoid that the particles are strongly fused.
  • the temperature range of the step (B) does not deviate from the temperature at which firing can be carried out, so in the step (B), an effect normally expected as firing, for example, an effect such as particle growth can be naturally obtained .
  • the lost crystallinity is recovered and improved by the subsequent firing in the step (B).
  • the temperature range of the step (B) it is possible to avoid that the particles are firmly fused. Therefore, when the fine particles are re-dispersed after firing, the fine particles can be easily crushed without giving strong energy.
  • the particles can be broken down with relatively weak energy, so there is no loss of crystallinity with the breaking up. Therefore, the fine particles pulverized to the small particle size in the (A) step recover crystallinity while undergoing the slight growth by the firing in the (B) step, and maintain the high crystallinity while still maintaining the small particle size. At the time of redispersion, it exhibits excellent dispersibility.
  • Such fine particles of the silicate compound of the present invention have a ratio (d 50 / d S ) of a primary particle diameter d S converted to a spherical particle from a specific surface area by a nitrogen adsorption method and a dispersed particle diameter d 50 of 1. It is 0 or more and less than 3.0.
  • the primary particle diameter d S converted to spherical particles is calculated by the reciprocal of the product of the specific surface area (surface area per unit mass) measured by the nitrogen adsorption method and the density of the silicate compound, as shown in the formula (1). it can.
  • the specific surface area by the nitrogen adsorption method can be measured according to a known method, and the density of the silicate compound can be derived based on the pycnometer method, the Archimedes method or the like.
  • d S n 1/1 (specific surface area (m 2 / g) density (g / m 3 )) (1) (Wherein, d S is the primary particle diameter converted to spherical particles and n is a constant)
  • the primary particle diameter d S converted to spherical particles represents the diameter of the primary particles regardless of the aggregation state of the fine particles in the dispersion medium. That is, according to the primary particle diameter d S converted to spherical particles, even when the fine particles are not much aggregated in the dispersion medium to become secondary particles, the same value as the value corresponding to the diameter of unaggregated primary particles A value will be obtained. Therefore, ideally, the value of the denominator of the ratio (d 50 / d S ) does not depend on the degree of aggregation or fusion of the fine particles in the dispersion medium.
  • the dispersed particle size d 50 is an average particle size when the dried fine particles are dispersed in a dispersion medium.
  • the particle diameter can be measured by various methods such as laser diffraction method, dynamic light scattering method and centrifugal sedimentation method, but in the present invention, the value measured by laser diffraction method is adopted as dispersed particle diameter as adopted in the examples.
  • d 50 As a dispersion medium, although water is mentioned typically, it does not specifically limit.
  • the dispersed particle size d 50 roughly corresponds to the secondary particle size.
  • the dispersed particle diameter d 50 has a value closer to the primary particle diameter d S converted to spherical particles. That is, the ratio (d 50 / d S ) approaches 1.0 as the degree of dispersion of the fine particles in the dispersion medium is higher.
  • the ratio (d 50 / d s ) is an indicator of the dispersibility of the particles and, from its principle, is 1.0 or more.
  • the ratio (d 50 / d S ) is close to 1.0 as in the silicate compound fine particles of the present invention, it means that the fine particles are well dispersed in the dispersion medium.
  • the ratio (d 50 / d S ) is less than 3.0 and the degree to which the fine particles are well dispersed in the dispersion medium is low, sufficient dispersibility in the resin can not be obtained. . If sufficient dispersibility in the resin can not be obtained, these fine particles can not be packed into the resin at a high density, so that the desired effect can not be obtained even when used as a filler.
  • the crystallite diameter calculated from the X-ray diffraction peak belonging to the (102) plane of the ⁇ -eucryptite phase is 45 nm or more and 100 nm or less. This type of X-ray diffraction peak can be measured by a known method.
  • the crystallite diameter is smaller than the above range, the original characteristics of the crystalline material can not be obtained. That is, with ⁇ -eucryptite, the effect of reducing CTE can not be obtained.
  • the crystallite diameter exceeds the above range, the progress of particle growth at the time of firing becomes remarkable, and it becomes difficult to maintain the diameter of the broken fine particles such that the diameter becomes small.
  • the crystallite diameter in the direction perpendicular to the diffractive surface is in the relationship of Formula (2) when it is expressed by 2 ⁇ (half width ⁇ , unit is Rad) corresponding to the peak width at half intensity.
  • L is the crystallite diameter
  • ⁇ is the X-ray wavelength (0.154 nm)
  • K is the form factor constant.
  • 0.9 is used for K.
  • L K ⁇ / ( ⁇ ⁇ cos ⁇ ) (2)
  • the silicate compound (forsterite) fine particles of the present invention have a primary particle diameter d S converted to spherical particles from the specific surface area by a nitrogen adsorption method, a dispersed particle diameter d 50 , Ratio (d 50 / d S ) is 1.0 or more and less than 3.0, and the crystallite diameter calculated from the X-ray diffraction peak belonging to the (112) plane of the forsterite phase is 30 nm or more and 100 nm or less .
  • Such forsterite fine particles can also be produced through processes including the steps (A) and (B), as in the case of the ⁇ -eucryptite fine particles. Even if the crystallinity of the silicate compound is lost by the pulverization of the raw material in the step (A), the lost crystallinity can be recovered and further improved by the subsequent firing of the step (B). In addition, according to the temperature range of the step (B), it is possible to avoid that the particles are firmly fused. Therefore, when the particles are redispersed after firing, the particles can be broken down with relatively weak energy, so that the crystallinity is not lost along with the crushing.
  • the fine particles pulverized to the small particle size in the (A) step recover crystallinity while undergoing the slight growth by the firing in the (B) step, and the high particle size still remains with the small particle size.
  • Such fine particles of the silicate compound of the present invention have a ratio (d 50 / d S ) of a primary particle diameter d S converted to a spherical particle from a specific surface area by a nitrogen adsorption method and a dispersed particle diameter d 50 of 1. It is 0 or more and less than 3.0.
  • the primary particle diameter d S and the dispersed particle diameter d 50 converted to spherical particles can be derived based on the same method as in the case of the ⁇ -eucryptite fine particles.
  • the ratio (d 50 / d S ) is in the range close to 1.0, it means that the fine particles are well dispersed in the dispersion medium.
  • the ratio (d 50 / d S ) is less than 3.0 and the degree to which the fine particles are well dispersed in the dispersion medium is low, sufficient dispersibility in the resin can not be obtained. In this case, since these fine particles can not be packed into the resin at high density, the desired effect can not be obtained even when used as a filler.
  • the crystallite diameter calculated from the X-ray diffraction peak belonging to the (112) plane of the forsterite phase is 30 nm or more and 100 nm or less. This type of X-ray diffraction peak can be measured by a known method.
  • the crystallite diameter calculated as described above is preferably 30 nm or more and 50 nm or less.
  • the crystallite diameter is in this range, it is easy to form fine particles of a silicate compound having a small particle diameter, excellent dispersibility in a resin, and high crystallinity.
  • the crystallite diameter is smaller than the above range, the original characteristics of the crystalline material can not be obtained. That is, in the forsterite, the effect of reducing the dielectric loss can not be obtained.
  • the crystallite diameter exceeds the above range, the progress of particle growth at the time of firing becomes remarkable, and it becomes difficult to maintain the diameter of the broken fine particles such that the diameter becomes small.
  • the crystallite diameter can be calculated by the above equation (2).
  • the silicate compound (raw material) is added so that the dispersed particle diameter d 50 is in the range of 0.1 ⁇ m to 2.0 ⁇ m. It has the process (A) which grind
  • the silicate compound used as a raw material can be manufactured by a well-known method in a process (A), and a commercial item can also be used.
  • a commercial item can also be used.
  • ⁇ -eucryptite one manufactured by the method described in WO 2016/117248, or FE-200 manufactured by Marusu Gakuen Co., Ltd. can be used.
  • forsterite one manufactured by the method described in WO2016 / 117248, or one manufactured by Marusu Gakuen Co., Ltd. can be used. Even if it is any silicate compound, you may use together what was manufactured and a commercial item.
  • the particle diameter to which the raw material is to be ground is related to the dispersed particle diameter d 50 of the silicate compound fine particles finally obtained through the next step (B). Therefore, when the dispersed particle diameter d 50 of the raw material pulverized in the step (A) exceeds 2.0 ⁇ m, the particle diameter of the finally obtained silicate compound also becomes large. On the other hand, when the dispersed particle diameter d 50 is reduced to less than 0.1 ⁇ m in the step (A), the particles are likely to be firmly fused in the next step (B).
  • Examples of the method of pulverizing the raw material in the step (A) include wet pulverization such as a bead mill and dry pulverization such as a jet mill.
  • wet pulverization such as a bead mill and dry pulverization such as a jet mill.
  • wet grinding using a bead mill or the like as the dispersion medium, general-purpose materials such as water, isopropanol and methyl ethyl ketone can be used, but are not particularly limited.
  • wet grinding may be advantageous in some cases, but dry grinding may, of course, also be suitably employed.
  • the drying method may be, for example, vacuum drying with a vacuum dryer or the like, heat drying with a hot plate or the like, or lyophilization, but is not particularly limited.
  • the fine particles pulverized in the previous step (A) are fired at a temperature of 750 ° C. or more and less than 950 ° C. Even if the crystallinity of the silicate compound is lost by the pulverization of the raw material in the step (A), the lost crystallinity can be recovered and thus improved by the step (B), and the crystallite The diameter and x-ray diffraction intensity can also be increased.
  • the firing temperature in the step (B) is lower than the above range, the effect of firing can not be obtained. For example, the crystallinity does not improve and the particles do not grow.
  • the firing temperature in the step (B) is larger than the above range, fusion between particles and particle growth significantly progress, and the silicate compound becomes coarse particles. In this case, fine particles of silicate compound having a ratio (d 50 / d S ) of less than 3.0 can not be obtained. Not only that, in order to grind such strongly fused coarse particles, strong energy is required, and as a result, a reduction in crystallite diameter accompanying the grinding can not be avoided.
  • the irregular and angular particle shape is changed to a rounded particle shape.
  • the firing method in the step (B) is not particularly limited as long as it can heat the silicate compound fine particles at a temperature of 750 ° C. or more and less than 950 ° C.
  • the baking time of the step (B) is, for example, 30 minutes to 20 hours, but other times may be possible.
  • the production conditions may be varied depending on the type of the silicate compound. For example, when the silicate compound is ⁇ -eucryptite, the firing temperature can be 800 ° C. or more and less than 950 ° C. Of course, even when the silicate compound is forsterite, the firing temperature can be 800 ° C. or more and less than 950 ° C.
  • the silicate compound fine particles of the present invention can be produced.
  • Such fine particles of the silicate compound of the present invention are in the form of roundness, and the dispersed particle diameter d S is within a small range (for example, within the range of 0.1 ⁇ m to 2.0 ⁇ m). There is.
  • the dispersed particle diameter d 50 is larger than the above range, and excellent dispersibility in the resin can be ensured as compared with fine particles of an irregular shaped angular shape (fine particles as shown in the prior art), and high density It becomes possible to fill.
  • the silicate compound fine particles of the present invention have higher crystallinity than the fine particles as shown in the prior art. Therefore, for example, if the silicate compound is ⁇ -eucryptite, sufficient effect to reduce CTE as a composite resin can be expected, and if the silicate compound is forsterite, dielectric loss as a composite resin is reduced. Sufficient effects can be expected. Therefore, any silicate compound can be suitably used as a filler for a semiconductor sealing material or underfilling.
  • the fine particles of the silicate compound calcined in the above-mentioned step (B) are dispersed (C) so that the dispersed particle diameter d 50 is in the range of 0.1 ⁇ m to 2.0 ⁇ m. It is preferable to have
  • the firing temperature in the previous step (B) is suppressed to a relatively low temperature range, strong aggregation and fusion between particles are avoided. Since fine particles can be broken down with relatively weak energy, reduction in crystallite diameter and decrease in X-ray diffraction intensity hardly occur in the step (C), and high crystallinity can be maintained.
  • the particles can be broken down while maintaining high crystallinity until the dispersed particle diameter d 50 is close to the particles (primary particles) that have been crushed in the previous step (A),
  • the fine particles after firing can be dispersed in a dispersion medium.
  • the ratio (d 50 / d S ) can be easily made less than 3.0.
  • Examples of the dispersion method in the step (C) include wet pulverization such as a bead mill and dry pulverization such as a jet mill, but are not particularly limited.
  • wet pulverization such as a bead mill
  • dry pulverization such as a jet mill
  • wet grinding such as bead milling
  • general-purpose dispersion media such as water, isopropanol and methyl ethyl ketone can be used, but this is not particularly limited.
  • the fine particles (baked powder) subjected to the previous step (B) are dispersed in a composite resin such as an epoxy resin, they may be directly dispersed, or may be dispersed in another dispersion medium and then mixed. May be In the case of dispersion in a resin, a three-roll mill or the like can be preferably used, but it is not particularly limited.
  • X-ray source Cu, voltage: 40 kV, current: 15 mA, step width: 0.01 °, scan rate: 5 ° / min, divergence angle slit (DS), using Rigaku X-ray diffractometer MiniFlex 600 0.625 °, scattering slit (SS); 8.0 mm, light receiving slit (RS); OPEN, incident solar slit; 2.5 °, light receiving solar slit; measured at 2.5 °, X-ray diffraction I got the data.
  • SS scattering slit
  • RS light receiving slit
  • OPEN incident solar slit
  • 2.5 ° light receiving solar slit
  • measured at 2.5 ° X-ray diffraction I got the data.
  • ⁇ X-ray diffraction intensity> The X-ray diffraction data of each sample was subjected to background processing with automatic setting using analysis software PDXL-2 to measure the X-ray diffraction intensity.
  • PDXL-2 analysis software
  • the dispersed particle diameter d 50 (dispersed particle diameter d 50 by laser diffraction method) was measured using a laser diffraction type particle size distribution measurement device Mastersizer 2000 manufactured by Malvern. In the measurement, pure water was used as a dispersion medium, and ultrasonic waves were irradiated for 1 minute.
  • a laser diffraction type particle size distribution measurement device Mastersizer 2000 manufactured by Malvern In the measurement, pure water was used as a dispersion medium, and ultrasonic waves were irradiated for 1 minute.
  • an average particle diameter calculated using a refractive index of 1.55 and an absorption coefficient (imaginary part) of 0.1 was employed.
  • For forsterite an average particle diameter calculated using a refractive index of 1.65 and an absorption coefficient (imaginary part) of 0.1 was employed.
  • the obtained mixture was subjected to an inlet temperature of 185 ° C., an atomizing air pressure of 0.14 MPa, an aspirator flow rate of 0.50 m 3 / min, using a spray dryer (Palvis Mini Spray GB 210-A, manufactured by Yamato Scientific Co., Ltd.). The mixture was dried under the conditions of a liquid transfer rate of 4 g / min to obtain a dry powder.
  • the outlet temperature at this time was 80 ⁇ 3 ° C.
  • the obtained dried powder was put in an alumina crucible and baked at a temperature of 850 ° C. for 5 hours in the atmosphere using a tabletop electric furnace to obtain 103 g of a white powder.
  • Primary particle diameter d S by nitrogen adsorption method 2.72Myuemu, dispersed particles size d 50 by a laser diffraction method was 11.2 .mu.m.
  • Example 1 40 g of ⁇ -eucryptite powder produced in Production Example 1, 160 g of isopropanol, and 900 g of ⁇ 0.5 mm zirconia beads were placed in a grinding container, and wet-milled under conditions of 1000 rpm using a bead mill apparatus Easy Nano RMB type manufactured by Imex. After grinding for 5 hours, the zirconia beads were removed and the slurry was recovered.
  • the slurry was then placed in an eggplant flask and dried at 10 Torr using a rotary evaporator until volatiles were eliminated to obtain a dry powder.
  • Primary particle diameter d S by a nitrogen adsorption method is 0.20 [mu] m, dispersed particles size d 50 by a laser diffraction method was 0.39 .mu.m.
  • the dried powder was put in an alumina sagger, heated to 850 ° C. at 3 ° C./min in a table electric furnace, and fired for 5 hours to obtain a fired powder.
  • the slurry was dried by the same method as described above to obtain a powder of ⁇ -eucryptite fine particles.
  • Primary particle diameter d S by a nitrogen adsorption method was 0.33 .mu.m
  • dispersed particles size d 50 by a laser diffraction method was 0.35 .mu.m. Further, when the particle morphology was observed with an electron microscope, rounded fine particles were confirmed.
  • Example 2 A slurry obtained by adding 100 g of the ⁇ -eucryptite powder produced in Production Example 1 to 400 g of isopropanol was prepared using a bead mill Ultra Apex Mill UAM 015 manufactured by Hiroshima Metal & Machinery Co., Ltd. The slurry was ground for 5 hours and 30 minutes under the condition of 5 m / sec in peripheral speed.
  • the slurry was then placed in an eggplant flask and dried at 10 Torr using a rotary evaporator until volatiles were eliminated to obtain a dry powder.
  • the primary particle diameter d S by the nitrogen adsorption method was 0.16 ⁇ m, and the dispersed particle diameter d 50 by the laser diffraction method was 0.30 ⁇ m.
  • the dried powder was put into an alumina sagger, heated to 850 ° C. at 3 ° C./min in a table electric furnace, and fired for 3 hours to obtain a fired powder.
  • the slurry was dried by the same method as described above to obtain a powder of ⁇ -eucryptite fine particles.
  • the primary particle diameter d S by the nitrogen adsorption method was 0.28 ⁇ m
  • the dispersed particle diameter d 50 by the laser diffraction method was 0.28 ⁇ m. Further, when the particle morphology was observed with an electron microscope, rounded fine particles were confirmed.
  • Example 3 40 g of commercially available ⁇ -eucryptite powder FE-200 (manufactured by Marusu Gakuen Co., Ltd.), 160 g of isopropanol, and 900 g of ⁇ 0.5 mm zirconia beads are placed in a grinding container, and a bead mill apparatus Easy Nano RMB type manufactured by Imex Co., Ltd. Wet grinding was performed under the conditions. After grinding for 5 hours, the zirconia beads were removed and the slurry was recovered.
  • the slurry was then placed in an eggplant flask and dried at 10 Torr using a rotary evaporator until volatiles were eliminated to obtain a dry powder.
  • the primary particle diameter d S by the nitrogen adsorption method was 0.19 ⁇ m, and the dispersed particle diameter d 50 by the laser diffraction method was 0.39 ⁇ m.
  • the dried powder was put in an alumina sagger, heated to 850 ° C. at 3 ° C./min in a table electric furnace, and fired for 5 hours to obtain a fired powder.
  • the slurry was dried by the same method as described above to obtain a powder of ⁇ -eucryptite fine particles.
  • Primary particle diameter d S by a nitrogen adsorption method was 0.34 .mu.m
  • dispersed particles size d 50 by a laser diffraction method was 0.42 .mu.m. Further, when the particle morphology was observed with an electron microscope, rounded fine particles were confirmed.
  • Example 4 40 g of forsterite powder produced in Production Example 2, 160 g of methanol, and 900 g of ⁇ 0.5 mm zirconia beads were placed in a grinding container, and wet ground under conditions of 1000 rpm using a bead mill apparatus Easy Nano RMB type manufactured by Imex. After grinding for 5 hours, the zirconia beads were removed and the slurry was recovered.
  • the slurry was then placed in an eggplant flask and dried at 10 Torr using a rotary evaporator until volatiles were eliminated to obtain a dry powder.
  • Primary particle diameter d S by a nitrogen adsorption method was 0.03 .mu.m
  • dispersed particles size d 50 by a laser diffraction method was 0.22 [mu] m.
  • the dried powder was put in an alumina sagger, heated to 900 ° C. at 3 ° C./min in a table-top electric furnace, and fired for 5 hours to obtain a fired powder.
  • the slurry was dried by the same method as described above to obtain a powder of forsterite fine particles.
  • Primary particle diameter d S by a nitrogen adsorption method was 0.07 .mu.m
  • dispersed particles size d 50 by a laser diffraction method was 0.19 .mu.m. Further, when the particle morphology was observed with an electron microscope, rounded fine particles were confirmed.
  • Comparative Example 1 The synthesis of ⁇ -eucryptite powder was performed in the same manner as in Production Example 1. 40 g of this ⁇ -eucryptite powder, 160 g of isopropanol, and 900 g of ⁇ 0.5 mm zirconia beads were placed in a crushing container, and wet-milled under conditions of 1000 rpm using a bead mill apparatus Easy Nano RMB type manufactured by Imex. After grinding for 5 hours, the zirconia beads were removed to obtain a slurry containing ⁇ -eucryptite fine particles.
  • Comparative Example 2 A slurry obtained by adding 100 g of the ⁇ -eucryptite powder produced in Production Example 1 to 400 g of isopropanol was prepared using a bead mill Ultra Apex Mill UAM 015 manufactured by Hiroshima Metal & Machinery Co., Ltd. The slurry was ground for 5 hours and 30 minutes under the condition of 5 m / sec in peripheral speed.
  • the slurry was then placed in an eggplant flask and dried at 10 Torr using a rotary evaporator until volatiles were eliminated to obtain a dry powder.
  • the primary particle diameter d S by the nitrogen adsorption method was 0.16 ⁇ m, and the dispersed particle diameter d 50 by the laser diffraction method was 0.30 ⁇ m. In addition, when the particle form was observed with an electron microscope, irregular and angular fine particles were confirmed.
  • Comparative Example 3 60 g of the ⁇ -eucryptite powder produced in Production Example 1, 240 g of isopropanol, and 1200 g of ⁇ 0.5 mm zirconia beads were placed in a grinding container, and wet ground under conditions of 1000 rpm using a bead mill apparatus Easy Nano RMB type manufactured by Imex. After grinding for 5 hours, the zirconia beads were removed to obtain a slurry containing ⁇ -eucryptite fine particles.
  • the slurry was then placed in an eggplant flask and dried at 10 Torr using a rotary evaporator until volatiles were eliminated to obtain a dry powder.
  • the primary particle diameter d S by the nitrogen adsorption method was 0.17 ⁇ m, and the dispersed particle diameter d 50 by the laser diffraction method was 0.32 ⁇ m.
  • the dried powder was put in an alumina sagger, heated to 700 ° C. at 3 ° C./min in a table-top electric furnace, and fired for 5 hours to obtain a fired powder.
  • irregular and angular fine particles were confirmed.
  • Comparative Example 4 A fired powder was obtained in the same manner as in Comparative Example 3 except that the temperature of the firing step was changed to 950 ° C.
  • the slurry was then placed in an eggplant flask and dried at 10 Torr using a rotary evaporator until volatiles were eliminated to obtain a dry powder.
  • Primary particle diameter d S by a nitrogen adsorption method was 0.95 .mu.m, dispersed particles size d 50 by a laser diffraction method is 78 .mu.m, was dispersed in a range of 0.1 [mu] m ⁇ 2.0 .mu.m.
  • irregular and angular fine particles were confirmed.
  • Comparative Example 5 40 g of forsterite powder produced in Production Example 2, 160 g of isopropanol, and 900 g of ⁇ 0.5 mm zirconia beads were placed in a grinding container, and wet ground under conditions of 1000 rpm using a bead mill apparatus Easy Nano RMB type manufactured by Imex. After grinding for 5 hours, the zirconia beads were removed to obtain a slurry containing forsterite fine particles.
  • the slurry was then placed in an eggplant flask and dried at 10 Torr using a rotary evaporator until volatiles were eliminated to obtain a dry powder.
  • Primary particle diameter d S by a nitrogen adsorption method is 0.03 .mu.m
  • the dispersed particles size d 50 by a laser diffraction method was 0.22 [mu] m.
  • the dried powder was put in an alumina sagger, heated to 700 ° C. at 3 ° C./min in a table-top electric furnace, and fired for 5 hours to obtain a fired powder.
  • irregular and angular fine particles were confirmed.
  • the fine particles of the silicate compound ( ⁇ -eucryptite) of Examples 1 to 3 each have a crystallite diameter of about 1.5 times (Example 1), after undergoing calcination (Step (B)), It was confirmed to grow 1.9 times (Example 2) and 1.5 times (Example 3).
  • Comparative Example 3 in which the firing temperature was 700 ° C., almost no particle growth was observed, and the particle growth was 1.1 times or less.
  • Comparative Example 4 in which the firing temperature was 950 ° C. it was confirmed that the particles grew up to about twice.
  • the ratio (d 50 / d) of the primary particle diameter d S converted to the spherical particle from the specific surface area by the nitrogen adsorption method and the dispersed particle diameter d 50 d S ) was 1.0 or more and less than 3.0, and the crystallite diameter calculated from the X-ray diffraction peak belonging to the (102) plane of the ⁇ -eucryptite phase was 45 nm or more and 100 nm or less.
  • the crystallite diameter is not less than 3.0 and is not less than 30 nm and not more than 100 nm, which is calculated from the X-ray diffraction peak belonging to the (112) plane of the forsterite phase.
  • the fine particles of the silicate compound of the present invention have a small particle diameter and are excellent in dispersibility in a resin, so that the resin can be filled at a higher density than in the past.
  • the fine particles of the silicate compound of the present invention have high crystallinity, the original characteristics of the material can be sufficiently exhibited. Therefore, for example, ⁇ -eucryptite fine particles can be suitably used as a filler for reducing CTE in applications such as semiconductor sealing materials and underfills.
  • it is a forsterite fine particle, it can be conveniently used as a filler for reducing a dielectric loss in uses, such as a semiconductor sealing material.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

Ces microparticules de composé de silicate ont un rapport (d5 0 /ds) du diamètre de particule dispersée (d50) au diamètre de particule primaire (ds) d'au moins 1,0 mais inférieur à 3,0, où d50 et ds sont dérivés de la conversion en particules sphériques à partir de la surface spécifique mesurée par la méthode d'adsorption d'azote. Les particules ont également un diamètre de particule cristallin de 45 à 100 nm tel que calculé à partir du pic de diffraction des rayons X attribué au plan (102) de la phase β-eucryptite.
PCT/JP2018/027107 2017-07-20 2018-07-19 Microparticules de composé de silicate et leur méthode de production WO2019017435A1 (fr)

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WO2022024708A1 (fr) * 2020-07-29 2022-02-03 京セラ株式会社 Serveur de gestion d'énergie électrique, et procédé de gestion d'énergie électrique

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JPH03197311A (ja) * 1989-12-25 1991-08-28 Tokuyama Soda Co Ltd 金属酸化物粒子の製造方法
JPH1179729A (ja) * 1997-09-08 1999-03-23 Chichibu Onoda Cement Corp ウォラストナイト微粒子の製造方法
WO2015146961A1 (fr) * 2014-03-25 2015-10-01 日産化学工業株式会社 Procédé de production de particules fines de forstérite
WO2016021688A1 (fr) * 2014-08-07 2016-02-11 日産化学工業株式会社 Microparticules de forstérite traitées au silane ainsi que procédé de fabrication de celles-ci, et liquide de dispersion de solvant organique de microparticules de forstérite traitées au silane ainsi que procédé de fabrication de celui-ci
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JPH03197311A (ja) * 1989-12-25 1991-08-28 Tokuyama Soda Co Ltd 金属酸化物粒子の製造方法
JPH1179729A (ja) * 1997-09-08 1999-03-23 Chichibu Onoda Cement Corp ウォラストナイト微粒子の製造方法
WO2015146961A1 (fr) * 2014-03-25 2015-10-01 日産化学工業株式会社 Procédé de production de particules fines de forstérite
WO2016021688A1 (fr) * 2014-08-07 2016-02-11 日産化学工業株式会社 Microparticules de forstérite traitées au silane ainsi que procédé de fabrication de celles-ci, et liquide de dispersion de solvant organique de microparticules de forstérite traitées au silane ainsi que procédé de fabrication de celui-ci
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022024708A1 (fr) * 2020-07-29 2022-02-03 京セラ株式会社 Serveur de gestion d'énergie électrique, et procédé de gestion d'énergie électrique

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