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• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/51—Particles with a specific particle size distribution
• • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/10—Solid density
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/003—Additives being defined by their diameter
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/011—Nanostructured additives

Definitions

• the present invention relates to a novel silica powder, a resin composition and a dispersion. More specifically, the present invention relates to a silica powder having an excellent filling property, in which the particle size and the particle size distribution are controlled.
• the present invention particularly provides a novel silica powder that can be suitably used as a filler to be added to a resin composition used for a semiconductor encapsulant or the like.
• fillers added to semiconductor encapsulants and semiconductor mounting adhesives represented by epoxy resin compositions have been developed.
• the particle size tends to decrease.
• the filler has a specific surface area of Mitsumi
• amorphous silica powder having a particle size of 100 n or more and 600 n or less in terms of primary particle size has been used.
• the existing amorphous silica powder having the above-mentioned specific surface area is generally poor in dispersibility due to its strong cohesiveness, resulting in a large dispersed particle size and further a particle size distribution during dispersion.
• a resin composition using such an amorphous silica powder has coarse particles derived from the filler, and causes poor penetration of the resin, which does not sufficiently penetrate into the gap during molding.
• the Mitsunita specific surface area is in the range of 5 or more and 20 2 /9 or less as in the conventional case, but the cohesiveness is extremely weak and the dispersibility is excellent. Therefore, a hydrophilic dry silica powder having a small dispersed particle size and a narrow particle size distribution at the time of dispersion has been proposed (Patent Document 1). Further, the silica powder described in Patent Document 2 has also been proposed.
• Patent Document 1 Japanese Unexamined Patent Publication "Japanese Unexamined Patent Publication No. 20 1 4-1 5 2 0 4 8" ⁇ 02020/175160 2 (: 170?2020/005618
• Patent Document 2 Japanese Patent Laid-Open Publication "Japanese Patent Laid-Open No. 2 017-1 1 9 6 2 1" Summary of Invention
• an object of the present invention is to provide a silica powder having a controlled particle size and particle size distribution and excellent filling properties. More specifically, it is intended to provide a silica powder which, when used as a resin filler, is capable of obtaining a resin composition having excellent gap permeability and low viscosity.
• the inventors of the present invention have proposed a burner, a reactor in which a burner is installed in silica obtained by burning a silicon compound in a flame, a flame condition and the like in a flame and a flame.
• a burner is installed in silica obtained by burning a silicon compound in a flame, a flame condition and the like in a flame and a flame.
• the present invention is a silica powder characterized by satisfying all of the following conditions (1) to (3).
• ⁇ is more than 300 ⁇ ! and less than 5001 ⁇ .
• ⁇ 100 is 30% or more and 45% or less.
• ⁇ 90 is the cumulative 90 mass% diameter of the mass-based particle size distribution obtained by the centrifugal sedimentation method.
• the resin composition containing the silica powder has excellent viscosity characteristics and excellent interstitial permeability. Can achieve both. Therefore, it is suitable as a filler for semiconductor encapsulants and semiconductor mounting adhesives. In particular, it can be suitably used as a filler for high-density mounting resin.
• FIG. 1 A schematic view of a main part of a reactor used for producing silica. MODE FOR CARRYING OUT THE INVENTION
• the silica powder of the present invention is produced by burning a silicon compound, and is a so-called “dry method (also referred to as a combustion method)”, which is a method for producing silica powder that grows and agglomerates in and near a flame. ] Is a silica powder obtained by
• ⁇ 100 is 30% or more and 45% or less.
• ⁇ 90 is the cumulative 90 mass% diameter of the mass-based particle size distribution obtained by the centrifugal sedimentation method.
• the viscosity of the product is low, the silica particle size is too large for the gap, resulting in voids when penetrating the gap, causing molding failure. In other words, sufficient narrow gap penetration cannot be obtained.
• the particle size is less than 300 n , the viscosity of the resin composition increases, which is not preferable. More preferably 330 n More than 400
• the packing characteristics of silica powder are loose and the bulk density is 250 More than 400 Specified by being 9 or less.
• the loose bulk density is a packing density when the silica powder is naturally dropped into a cup having a predetermined volume. Loose loose It is not preferable because the viscosity of the resin composition increases.
• Loose bulk density is 400 If it exceeds 3 , the viscosity of the resin composition will be low, but as a result of the silica particle size being too large in the gap, voids will be generated when the gap penetrates, causing defective molding. In other words, sufficient narrow gap permeability cannot be obtained.
• loose bulk density 270 9/3 or more, 3501 ⁇ 9 / Rei_1
• the characteristics that the particle size distribution is appropriately adjusted are the cumulative 50% mass diameter port 50 and the cumulative 90% mass diameter ⁇ 9 . Therefore, it is specified that ⁇ (0 9 ⁇ -0 5 ⁇ )/0 5 ⁇ 100 is 30% or more and 45% or less. If the particle size distribution represented by the above formula exceeds 45%, coarse particles will increase and cause voids. On the other hand, when the particle size distribution is less than 30%, the particle size distribution is narrow and loose, and the value of the bulk density becomes small, so that the viscosity is not lowered, which is not preferable. More preferably, ⁇ (0 9 ⁇ -0 5 ⁇ )/0 50 ⁇ 100 is 33% or more and 42% or less.
• the silica powder of the present invention has a geometric standard deviation 9 of the mass-based particle size distribution obtained by a centrifugal sedimentation method of 1.25 or more,...! .40 or less is preferable. If the geometric standard deviation 9 is small, it can be said that the particle size distribution is narrow, and thus the amount of coarse particles is reduced. However, the presence of a particle size distribution within a certain range tends to reduce the viscosity when added to the resin.
• the geometric standard deviation 9 is the cumulative standard particle size distribution obtained by the centrifugal sedimentation method. ⁇ 02020/175 160 5 (: 170?2020/005618
• the mass-based particle size distribution measured by the centrifugal sedimentation method is based on the hydrophilic dry silica powder.
• the elemental contents of iron, nickel, chromium, and aluminum be less than 1 because the short-circuit between metal wirings in the semiconductor device can be reduced.
• the silica powder of the present invention has a sodium ion, potassium ion, and chloride ion content measured by a hot water extraction method, each of which has an ion content of less than 1 is a malfunction of a semiconductor device. It is preferable because it can reduce the corrosion of the metal wiring in the semiconductor device.
• the particles constituting the silica powder of the present invention are preferably spherical.
• the shape can be grasped, for example, by observation with an electron microscope.
• the silica powder of the present invention has a ⁇ .
• the silica powder of the present invention has a median diameter aperture 5 as described above. Etc., so usually
• the use of the silica powder of the present invention as described above is not particularly limited.
• the silica powder of the present invention is, for example, a filler for a semiconductor encapsulating material or a semiconductor mounting adhesive, a filler for a dial attach film or a die attach paste, or a filler for a resin composition such as an insulating film of a semiconductor package substrate. It can be used as a material.
• the silica powder of the present invention is preferably used as a filler for a resin composition for high density mounting.
• the resin used in the resin composition include resins known as resins for semiconductor encapsulants and adhesives, and specifically include epoxy resin, acrylic resin, silicone resin and the like.
• the silica powder of the present invention can be dispersed in a solvent to form a dispersion.
• the dispersion may be a liquid dispersion, or a solid obtained by solidifying such a dispersion.
• the solvent used for dispersing the silica powder is not particularly limited as long as it is a solvent in which the silica powder is easily dispersed.
• a solvent for example, water and organic solvents such as alcohols, ethers and ketones can be used. Examples of the alcohols include methanol, ethanol and isopropanol.
• the solvent a mixed solvent of water and one or more of the above organic solvents may be used.
• a dispersing agent such as a surfactant, a thickener, a wetting agent, an antifoaming agent or an acidic or alkaline pH adjusting agent are added. May be. And the pH of dispersion is not limited.
• the silica powder of the present invention is a raw material for quartz products, abrasive grains of CMP (Chem i cal l Meehan i cal po li sh i ng) abrasive, toner external additive, additive for liquid crystal sealing material, It can also be used as a dental filling material or an ink jet coating agent, etc.
• the silica powder of the present invention is treated with at least one treatment agent selected from the group consisting of silylating agents, silicone oils, siloxanes, fatty acids, etc., depending on the application as described above. It may be used as a base material or a bulk material containing silica powder. ⁇ 02020/175160 7 ⁇ (: 170?2020/005618
• the silica powder of the present invention is a method for producing dry silica, which is produced by burning a silicon compound, grows in and near a flame, and is aggregated to obtain silica powder. It can be obtained by installing a PANA with a multi-tube structure in a reactor equipped with a jacket for cooling around it and adjusting the flame combustion conditions and cooling conditions. That is, the combustion condition of the flame is to control so that the oxygen content of the entire flame is large, and the cooling condition is to control so that the cooling rate of the flame is slowed down, so that the efficiency of the present invention is improved. Silica powder can be produced.
• Fig. 1 shows a schematic diagram of an apparatus for producing the silica powder of the present invention.
• the circumference of the concentric triple tube structure burner 1 is further covered with a cylindrical outer tube 2.
• the cylindrical outer tube 2 is regarded as the fourth tube of the burner 1
• the burner 1 is It can be regarded as having a quadruple pipe structure as a whole.
• the tubes that make up the concentric triple tube will be referred to as the "center tube,” “first annular tube,” and “second annular tube” in that order from the center to the outer edge.
• the burner 1 is installed in the reactor 3 in which a flame is burned, and a silicid force is generated from the silicon compound inside the burner 1.
• the reactor 3 has a jacket (not shown) on the outside so that the cooling medium can flow through it so that forced cooling can be performed.
• a silicon compound in a gaseous state and oxygen are premixed and introduced into the central tube of the triple tube.
• an inert gas such as nitrogen may also be mixed and mixed.
• the silicon compound is a liquid or a solid at room temperature, the silicon compound is heated and vaporized before use.
• silica is generated by the hydrolysis reaction of a silicon compound, a fuel that generates water vapor when it reacts with oxygen, such as hydrogen or hydrocarbon, is mixed together.
• an auxiliary flame is formed in the first annular pipe adjacent to the central pipe of the triple pipe. ⁇ 02020/175 160 8 ⁇ (: 17 2020/005618
• an inert gas such as nitrogen may be mixed and introduced.
• oxygen may also be mixed and mixed.
• oxygen is introduced into the second annular pipe adjacent to the outside of the first annular pipe of the triple pipe.
• This oxygen has two roles: formation of silica by reaction with silicon compounds and formation of auxiliary flame.
• an inert gas such as nitrogen may be mixed and mixed.
• a mixed gas of oxygen and an inert gas such as nitrogen is introduced into the space formed by the outer wall of the triple tube and the inner wall of the cylindrical outer cylinder 2. It is preferable to use air as the mixed gas because it is easy.
• a jacket portion is provided outside the reactor 3, and a refrigerant for removing combustion heat is circulated outside the system. Since the combustion gas mostly contains water vapor, in order to prevent corrosion of the reactor 3 caused by dew condensation of water vapor and subsequent absorption of the corrosive components in the combustion gas into the condensed water. It is a preferable mode that the temperature of the refrigerant before the absorption of the combustion heat (specifically, the temperature of the refrigerant introduced into the jacket) is set to 50 ° or more and 200 ° or less. Considering the ease of implementation, it is even more preferable to use hot water of 50° or more and 90° or less as the refrigerant.
• the difference between the temperature when the refrigerant is introduced into the jacket (inlet temperature) and the temperature of the refrigerant discharged from the jacket (outlet temperature) is calculated. From the amount of the generated refrigerant, the amount of heat absorbed by the refrigerant, that is, the amount of heat removed by the refrigerant from the reactor 3 can be grasped.
• the silica powder of the present invention it is particularly important to adjust the flame combustion condition and the cooling condition, as described below, and it is preferable to satisfy the following conditions.
• the silicon compound which is a raw material of the silica powder those which are gas, liquid or solid at room temperature are used without particular limitation.
• cyclic siloxanes such as octamethylcyclotetrasiloxane, chain siloxanes such as hexamethyldisiloxane, alkoxysilanes such as tetramethoxysilane, and chlorosilanes such as tetrachlorosilane can be used as silicon compounds.
• a silicon compound containing no chlorine in its molecular formula such as the above-mentioned siloxane and alkoxysilane, because chloride ions contained in the obtained silica powder can be significantly reduced.
• the silicon compound those having a small content of various metal impurities can be easily obtained. Therefore, by using such a silicon compound having a low content of metal impurities as a raw material, the amount of metal impurities contained in the produced silica powder can be reduced. Further, the amount of metal impurities contained in the produced silica powder can be further reduced by further purifying the arsenic compound by distillation or the like and using it as a raw material.
• the recovery of the silica powder of the present invention is not particularly limited, but it is performed by separating it from the combustion gas by filter separation with a sintered metal filter, ceramic filter, back filter or the like or centrifugal separation with a cyclone or the like. .. ⁇ 02020/175160 10 (: 170?2020/005618
• the number of concentric triple tubes used is one, but it is also possible to use a multiple tube system in which a plurality of concentric triple tubes are arranged, as shown in Examples described later.
• the multiple tube method it is important to obtain the silica powder of the present invention in terms of homogeneity by making the concentric triple tubes have the same structure and the same size and making the distance between the nearest centers of the concentric triple tubes the same. Is preferred.
• the cylindrical outer cylinder 2 may be installed so as to collectively cover a plurality of concentric triple tube manifolds.
• silica powder produced by burning a silicon compound liquid silica that is melted in a flame is spheroidized due to surface tension, and thus solid silica powder particles produced are Becomes a spherical shape close to a true sphere.
• the true density is theoretical density of silica 2.2. Matches approximately 3 Therefore, it mentioned above, silica powder produced by the production method of the silica powder of the present invention also, the shape is spherical, the true density is approximately 2.2 9 / ⁇ 3.
• the present invention is a silica powder characterized by satisfying all of the following conditions (1) to (3).
• ⁇ 100 is 30% or more and 45% or less.
• ⁇ 90 is the cumulative 90 mass% diameter of the mass-based particle size distribution obtained by the centrifugal sedimentation method.
• the geometric standard deviation 9 of the mass-based particle size distribution obtained by the centrifugal sedimentation method is 1.25 or more, and! It is preferably in the range of .40 or less.
• each element is less than 10!. ⁇ 02020/175160 11 ⁇ (: 170?2020/005618
• the ion content of each of sodium ion, potassium ion, and chloride ion which is measured by a hot water extraction method, is preferably less than 1.
• the present invention also provides a resin composition in which the silica powder of the present invention is filled in a resin, and a dispersion in which the silica powder of the present invention is dispersed in a solvent.
• a resin composition in which the silica powder of the present invention is filled in a resin
• a dispersion in which the silica powder of the present invention is dispersed in a solvent.
• Shibata Rikagaku's specific surface area measuring device 3 Nitrogen adsorption using 1 000, using the one-point method for the use of nitrogen. Was measured.
• a silica suspension having a silica concentration of 1.51% obtained by the above method was added to 0? 3 ⁇ 3 1
• the mass-standard particle size distribution was measured using a disk centrifugal type particle size distribution measuring instrument port I 2 ⁇ 0. Incidentally measurement conditions, the rotation number 9 0 0 0 "01, and a silica true density of 2. 2 9 / Rei_rei_1 3.
• the loosened bulk density and the firm bulk density were measured using a powder characteristic evaluation device, Powder Tester D1 X, manufactured by Hosokawa Micron Corporation.
• the "loose bulk density” in the present invention refers to the bulk density in a loosely packed state, in which a sample is placed in a cylindrical container (material: stainless steel) with a volume of 100! It is measured by feeding it uniformly from the top, scraping the top surface, and weighing.
• hard bulk density refers to the bulk density when tapping is added to this to make a dense packing.
• tapping is an operation in which the container filled with the sample is repeatedly dropped from a certain height to give a light impact to the bottom, and the sample is densely packed.
• the upper surface is cut off and weighed, and then a cap (equipment of Hosokawa Micron's powder-tester below) is put on this container, and the powder is added to this upper edge.
• tapping is performed 180 times. After the completion, remove the cap, scrape off the powder on the upper surface of the container, and weigh it. The bulk density in this state is taken as the bulk density.
• the dried silica powder 29 was precisely weighed and transferred to a platinum dish, and concentrated nitric acid 10 !_ and hydrofluoric acid 100 1 1_ were added in this order. This was placed on a hot plate set at 200° and heated to dry the contents. After cooling to room temperature, concentrated nitric acid 21_ was further added, and the solution was placed on a hot plate set at 200°C and heated to dissolve. After cooling to room temperature, the solution, which is the content of the platinum dish, is poured into a mes- ⁇ 02020/175160 13 ⁇ (: 170?2020/005618
• the sample was transferred to Sco, diluted with ultrapure water and adjusted to the marked line.
• the element contents of iron, nickel, chromium, and aluminum were measured by an optical emission spectrometer (manufactured by Shimadzu Corporation, model number: 0_3_100V).
• Silica powder 59 was added to ultrapure water 509, and the mixture was heated at 120 ° for 24 hours using a fluororesin decomposition vessel to perform hot water extraction of ions. For ultrapure water and silica powder, ⁇ . Weighed to the unit. Then, the solid content was separated using a centrifuge to obtain a measurement sample. The same operation was performed using only ultrapure water, and this was used as a blank sample for measurement.
• the silica powder 0.0 3 9 were weighed, after addition of ethanol 3_Rei ⁇ , using an ultrasonic cleaner, and dispersed for 5 minutes to obtain ethanol suspension. After dropping this suspension on a silicon wafer, it was dried and the field emission scanning electron microscope 3-5500 manufactured by Hitachi High-Technologies Corporation was used to observe the silica at 3 times IV! I confirmed.
• ⁇ is the distance between the center of the central tube and the center of another central tube (the length of the side of the equilateral triangle), is the inner diameter of the central tube, and the mouth is the center of the central tube and the inner wall of the reactor. Is the shortest distance between and. The larger the mouth /, the greater the distance between the flame and the inner wall of the reactor. ⁇ 02020/175160 15 ⁇ (: 170?2020/005618
• octamethylcyclotetrasiloxane was burned as described below to produce silica powder.
• the octamethylcyclotetrasiloxane will be simply referred to as a raw material.
• the mixture was introduced into the central tube of the concentric triple tube at 200°.
• hydrogen and nitrogen were mixed and introduced into the first annular pipe, which is the outermost tube adjacent to the central tube of the concentric triple tube.
• oxygen was introduced into the second annular pipe, which is the outermost peripheral pipe adjacent to the first annular pipe of the concentric triple tube.
• air was introduced into the space consisting of the outer wall of the second annular pipe of the concentric triple tube and the inner wall of the outer cylinder surrounding the concentric triple tube.
• Table 1 shows the production conditions and the characteristics of the obtained silica powder. Also, 1 ⁇ 1
• Table 1 shows the physical properties of the obtained silica powder. In each of the examples, the content of 6, 1 ⁇ ] ⁇ ”, eight, N 3 +, [ ⁇ + and ⁇ _- was all less than 1.
• Table 2 shows the physical properties of the obtained silica powder.

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