WO2020019277A1 - 一种球形粉体填料的制备方法、由此得到的球形粉体填料及其应用 - Google Patents
一种球形粉体填料的制备方法、由此得到的球形粉体填料及其应用 Download PDFInfo
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- WO2020019277A1 WO2020019277A1 PCT/CN2018/097327 CN2018097327W WO2020019277A1 WO 2020019277 A1 WO2020019277 A1 WO 2020019277A1 CN 2018097327 W CN2018097327 W CN 2018097327W WO 2020019277 A1 WO2020019277 A1 WO 2020019277A1
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- 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
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/06—Clay-free compositions
Definitions
- the invention relates to the packaging of semiconductors, and more particularly to a method for preparing a spherical powder filler, the spherical powder filler obtained thereby, and applications thereof.
- packaging materials such as plastic encapsulant, patch glue, underfill, and chip carrier board are required.
- passive components semiconductor components, electro-acoustic devices, display devices, optical devices and radio frequency devices into equipment, high-density inerconnect (HDI), high-frequency high-speed boards, and motherboards must be used.
- Such packaging materials and circuit boards are generally mainly composed of organic polymers such as epoxy resins and fillers, where the fillers are mainly angular or spherical silica, whose main function is to reduce the thermal expansion coefficient of organic polymers.
- the existing filler is selected from spherical silica for tight filling gradation.
- the chemical structure of the silica is the Q unit of Si, namely SiO 4- .
- the signal frequency used by semiconductors is getting higher and higher, and the increase in signal transmission speed and low loss requires fillers with low induction rate and low induction loss.
- the electrical induction rate and electrical induction loss of the material basically depend on the chemical composition and structure of the material. Silica has its inherent electrical induction rate and electrical induction loss value. Therefore, the existing filler cannot meet the lower requirements. Requirements for induction rate and low induction loss.
- spherical silica is generally made by high-temperature dry processes such as the flame melting method and the metal silicon powder deflagration method, which are easily mixed with conductive foreign materials such as iron. It is difficult to avoid the inclusion of coarse particles and conductive foreign materials. . Moreover, once coarse particles and conductive foreign matter are mixed in, they cannot be removed dryly. Therefore, the existing fillers cannot meet the requirements of no conductive foreign matter and no coarse particles.
- fused spherical low-radiation silica is selected from natural quartz ore. It is made by smelting and melting and spheroidizing after pickling and purifying sand, so its purity depends to a large extent on the purity of the natural mineral itself. Therefore, the existing fillers cannot meet the requirements of low radioactivity.
- the invention aims to provide a method for preparing a spherical powder filler, the spherical powder filler obtained thereby, and applications thereof.
- the filler provided thereby has low electromotive force, low electromotive loss, no conductive foreign matter, and no coarse particles. And low radioactivity.
- the invention provides a method for preparing a spherical powder filler, comprising the steps of: S1, providing a spherical siloxane having a composition of 0-10% by weight of Q units and 90-100% by weight of T units; S2, the spherical siloxane Heat treatment, so that the silanol groups in the spherical siloxane are condensed to obtain the condensed silicone; and S3, a treatment agent is added to perform surface treatment on the condensed silicone to eliminate the silanol groups in the condensed siloxane to obtain a spherical shape Powder filler.
- the weight percentage of the treatment agent is 0.5-50 wt%.
- R 1 , R 2 , R 3 , R 4 , and R 5 in the T unit represent the same or different organic groups
- R a1 , R b1 , R a2 , R b2 , R a3 , and R b3 in the D unit represent the same or different Different organic groups
- R c1 , R d1 , R e1 , R c2 , R d2 , and R e2 in the M unit represent the same or different organic groups.
- the silica of the spherical powder filler of the present invention is a T-unit, and the introduction of organic groups R 1 , R 2 , R 3 , R 4 , and R 5 greatly reduces the induced electricity. Rate and induced loss.
- the T unit since the T unit has only three SiOSi bridging points and the thermal expansion coefficient is higher than that of the Q unit silica, an appropriate amount of Q units can be introduced to adjust the balance of the induction rate, induction loss, and thermal expansion coefficient as needed.
- the condensation siloxane obtained by heat treatment has a high degree of condensation by heating, due to space geometric constraints, new isolated surface Si-OH and internal Si-OH will be generated, so the D-forming
- the treating agent is used to condense the Si-OH in the condensation siloxane, and / or adding a treating agent that generates M units to cap the Si-OH in the condensing siloxane, thereby further reducing the electric induction rate and the electric loss.
- step S1 methyltrimethoxysilane and / or phenyltrimethoxysilane and tetraethoxysilane are used as raw materials to provide a spherical siloxane.
- the composition of the spherical siloxane in step S1 is 96-99.9% by weight of T units and 0.1-4% by weight of Q units.
- step S2 the heat treatment is achieved by electric heating or microwave heating, which causes Si-OH in the spherical siloxane to condense to produce a SiOSi structure.
- the equation of the condensation reaction is as follows:
- the heat treatment temperature in step S2 is 180-650 degrees. More preferably, the temperature is 250-550 degrees. Most preferably, the temperature is 280-380 degrees. It should be understood that too low temperature will lead to incomplete condensation reaction of Si-OH, while too high temperature will cause decomposition of organic groups. For example, because the decomposition temperature of phenyl is high, when the organic group is a phenyl group, the corresponding heat treatment temperature is higher than when the organic group is an alkyl group. In a preferred embodiment, the heat treatment time is 30 minutes or more and 24 hours or less. It should be understood that the shorter the time required for higher temperatures, and the longer the time required for lower temperatures.
- the processing agent that generates D units causes Si-OH in the condensation siloxane to further condense to produce a SiOSi structure.
- the equation of the condensation reaction is as follows:
- the processing agent that generates D units is selected from at least one of the group consisting of: (CH 3 ) 2 Si (OCH 3 ) 2 , (CH 3 ) 2 Si (OCH 2 CH 3 ) 2 , ( CH 3 ) HSi (OCH 3 ) 2 , (CH 3 ) HSi (OCH 2 CH 3 ) 2 , H 2 Si (OCH 3 ) 2 , H 2 Si (OCH 2 CH 3 ) 2 , (C 6 H 5 ) 2 Si (OCH 3 ) 2 , (C 6 H 5 ) 2 Si (OCH 2 CH 3 ) 2 , C 6 H 5 CH 3 Si (OCH 3 ) 2 , C 6 H 5 CH 3 Si (OCH 3 ) 2 , C 6 H 5 CH 3 Si (OCH 2 CH 3 ) 2 , C 6 H 5 CH 3 Si (OCH 2 CH 3 ) 2 , C 6 H 5 HSi (OCH 3 ) 2 , C 6 H 5 HSi (OCH 2 CH 3 )
- the processing agent generating M units causes the Si-OH in the condensation siloxane to further condense to produce a SiOSi structure.
- the equation of the condensation reaction is as follows:
- the processing agent that generates M units is at least one selected from the group consisting of: (CH 3 ) 3 SiNHSi (CH 3 ) 3 , (CH 3 ) 2 C 6 H 5 SiNHSi (CH 3 ) 2 C 6 H 5 , CH 3 (C 6 H 5 ) 2 SiNHSiCH 3 (C 6 H 5 ).
- the treating agent further includes a silane coupling agent to further eliminate Si-OH in the condensation siloxane.
- the silane coupling agent is at least one selected from the group consisting of an epoxy silane coupling agent, an aliphatic aminosilane coupling agent, an aromatic aminosilane coupling agent, methacrylic acid Acyloxypropylsilane coupling agent, acryloxypropylsilane coupling agent, ureidopropylsilane coupling agent, chloropropylsilane coupling agent, mercaptopropylsilane coupling agent, polysulfide-based silane coupling Crosslinking agent, isocyanate propylsilane coupling agent, etc.
- the silane coupling agent may be processed after the treatment agent generating D units and / or M units is processed, or may be used together with the treatment agent generating D units and / or M units.
- the weight percentage of the treating agent is 1-50 wt%.
- the treatment agent is a separate component treatment agent, such as hexamethyldisilazane, dimethyldimethoxysilane, or dimethyldichlorosilane.
- the treatment agent is a mixed treatment agent, such as dimethyldimethoxysilane (such as 70% by weight) and hexamethyldisilazane (such as 30% by weight), vinyldimethoxy Silane (such as 50% by weight) and hexamethyldisilazane (such as 50% by weight), or 3- (2,3-glycidoxypropyl) trimethoxysilane (such as 30% by weight) and six Methyldisilazane (e.g. 70% by weight).
- dimethyldimethoxysilane such as 70% by weight
- hexamethyldisilazane such as 30% by weight
- vinyldimethoxy Silane such as 50% by weight
- hexamethyldisilazane such as 50% by weight
- 3- (2,3-glycidoxypropyl) trimethoxysilane such as 30% by weight
- six Methyldisilazane e.g. 70% by weight
- the preparation method includes using dry or wet sieving or inertial classification to remove coarse particles above 75 microns in the spherical powder filler.
- coarse particles larger than 55 microns are removed from the spherical powder filler.
- coarse particles larger than 45 microns are removed from the spherical powder filler.
- coarse particles above 20 microns are removed from the spherical powder filler.
- coarse particles larger than 10 microns are removed from the spherical powder filler.
- coarse particles larger than 5 microns are removed from the spherical powder filler.
- coarse particles larger than 3 microns are removed from the spherical powder filler.
- coarse particles larger than 1 micron in the spherical powder filler are removed.
- the present invention also provides a spherical powder filler obtained according to the above preparation method, and the particle size of the spherical powder filler is 0.1-50 microns. Preferably, the particle size is 0.5-30 microns.
- the measurement results show that the electromotive force of the spherical powder filler of the present invention at 500 MHz is only 2.5-2.8, which is less than 3, and the electromotive force of the conventional Q-unit silica filler is approximately 3.8-4.5. Therefore, the spherical powder filler of the present invention has a greatly reduced electric induction rate, and can meet the material requirements for high-frequency signals in the 5G era.
- the measurement results show that the electrokinetic loss of the spherical powder filler of the present invention at 500 MHz is only 0.0005 to 0.002, which is less than 0.005, and the electrokinetic loss of the conventional Q unit silica filler is approximately 0.003-0.01. Therefore, the spherical powder filler of the present invention has greatly reduced induction loss, and can meet the material requirements for high-frequency signals in the 5G era.
- the thermal expansion coefficient of the spherical powder filler of the present invention is 5-15 ppm, while the thermal expansion coefficient of the existing fused silica is about 0.5 ppm, and the crystalline silica (quartz) is 8 to 13 ppm. Therefore, the thermal expansion coefficient of the spherical powder filler of the present invention is equivalent to the thermal expansion coefficient of general inorganic fillers, and can meet the material requirements for high-frequency signals in the 5G era.
- the present invention further provides an application of the spherical powder filler according to the above, wherein spherical powder fillers of different particle sizes are closely packed and graded in a resin to form a composite material.
- the composite material is suitable for a semiconductor packaging material, a circuit board and an intermediate semi-finished product thereof.
- the packaging material is a plastic encapsulant, a patch glue, an underfill, or a chip carrier board.
- the molding compound is a molding compound in the form of DIP, a molding compound in the form of SMT, a molding compound in MUF, FO-WLP, and FCBGA.
- the circuit board is an HDI, a high-frequency high-speed board, or a motherboard.
- ⁇ Thermal expansion coefficient of composite material
- V 1 Volume fraction of resin
- ⁇ 1 Thermal expansion coefficient of resin
- V 2 Volume fraction of filler
- ⁇ 2 Thermal expansion coefficient of filler.
- the thermal expansion coefficient ⁇ 1 of the resin is 60 to 120 ppm.
- the thermal expansion coefficient ⁇ 2 of the spherical powder filler of the present invention is much lower than the thermal expansion coefficient of the resin at 5 to 15 ppm. It can reduce the resin composition after curing like the existing inorganic filler.
- the coefficient of thermal expansion is matched with the thermal expansion of the wire metal or wafer. Therefore, by adjusting the volume fraction of the resin and the spherical powder filler, the thermal expansion coefficient required by the composite material can be designed according to the needs to form a packaging material, a circuit board and its intermediate semi-finished product.
- ⁇ Dielectric of the composite
- V 1 resin volume fraction
- ⁇ 1 YUDEN of resin
- V 2 volume fraction of filler
- ⁇ 2 the filler Yuden rate.
- the electrical loss of the composite material is determined by the electrical loss of the resin and filler, and the number of polar groups on the surface of the filler.
- the spherical powder filler according to the present invention has a low electromotive force, and the fewer polar groups it has on the surface of the filler, therefore, the composite material has a low electromotive loss.
- the filler obtained by the method for preparing a spherical powder filler according to the present invention has a low induction rate and a low induction loss.
- the raw materials of the preparation method are organic materials, which do not involve angular crushed quartz that is commonly used, and can be refined by industrial methods such as distillation, the spherical powder filler formed does not contain radioactive elements such as uranium and plutonium, so it meets no Requirements for conductive foreign bodies, no coarse particles, and low radioactivity.
- the synthesis parameters can be appropriately adjusted to produce a spherical powder filler having a particle diameter of 0.1 to 50 microns.
- the average particle diameter was measured with a laser particle size analyzer LA-700 from HORIBA.
- the solvent is isopropanol;
- the specific surface area was measured by FlowSorbIII2305 of SHIMADZU;
- Uranium and plutonium content were determined by Agilent 7700X ICP-MS.
- the sample preparation method is to prepare the sample completely with hydrofluoric acid after burning at 800 degrees;
- Q units and T units are calculated from the frontal integrated area in the range of -80 to -120 ppm and the frontal integrated area in the range of -30 to -80 ppm on the solid 28 Si-NMR nuclear magnetic resonance spectrum.
- the induction rate and the induction loss were measured by KEYCOM's perturbation method, sample cavity closed cavity resonance method, induction rate, induction loss measurement device Model No. DPS18.
- methyltrimethoxysilane and tetraethoxysilane as raw materials, refer to Japanese patents P2001-192452A, P2002-322282A, JP-A-6-49209, JP-A-6-279589, and P2000-345044A to make different compositions. Spherical silicone.
- the spherical siloxane was heat-treated at 350 ° C for one hour.
- the heat-treated spherical siloxane was subjected to a surface treatment by a dry method, and the treatment agent was hexamethyldisilazane.
- the sample was dried at 150 ° C for 3 hours after the treatment.
- Hexamethyldisilazane treatment amount (%) i.e. weight percentage added amount
- weight percentage added amount (weight of hexamethyldisilazane / (weight of hexamethyldisilazane + weight of spherical siloxane)) ⁇ %.
- the samples obtained according to Examples 1 to 5 are all less than 3 inductive rate and less than 0.005 inductive loss, so as to meet the low inducement rate (small signal delay) and low inducement loss of fillers in the 5G era. (Less signal loss).
- methyltrimethoxysilane and tetraethoxysilane as raw materials, refer to the methods of Japanese Patent P2001-192452A, P2002-322282A, JP-A-6-49209, JP-A-6-279589, and P2000-345044A to make the average particle size. 2 micron spherical siloxane.
- the spherical siloxane was heat-treated in an electric furnace at different temperatures for 1 hour.
- the heat-treated spherical siloxane was subjected to a surface treatment by a dry method, and the treatment agent was hexamethyldisilazane.
- the sample was dried at 150 ° C for 3 hours after the treatment.
- Hexamethyldisilazane treatment amount (%) (weight of hexamethyldisilazane / (weight of hexamethyldisilazane + weight of spherical siloxane)) ⁇ %.
- the synthesis and determination results are listed in the following Table 2:
- the samples obtained according to Examples 6 to 8 are all less than 3 inductive rate and less than 0.005 inductive loss, so as to meet the low inducement rate (small signal delay) and low inductive loss of fillers in the 5G era. (Less signal loss).
- phenyltrimethoxysilane and tetraethoxysilane as raw materials, refer to the methods in Japanese Patent P2001-192452A, P2002-322282A, JP-A-6-49209, JP-A-6-279589, and P2000-345044A to make the average particle size. 2 micron spherical siloxane.
- the spherical siloxane was heat-treated in an electric furnace at different temperatures for 1 hour.
- the heat-treated spherical siloxane was subjected to a surface treatment by a dry method, and the treatment agent was hexamethyldisilazane.
- the sample was dried at 150 ° C for 3 hours after the treatment.
- Hexamethyldisilazane treatment amount (%) (weight of hexamethyldisilazane / (weight of hexamethyldisilazane + weight of spherical siloxane)) ⁇ %.
- the synthesis and determination results are listed in Table 3 below:
- the samples obtained according to Examples 9 to 11 are all less than 3 inductive rate and less than 0.005 inductive loss, so as to meet the low inducement rate (small signal delay) and low inducement loss of fillers in the 5G era. (Less signal loss).
- methyltrimethoxysilane and tetraethoxysilane as raw materials, refer to the methods of Japanese Patent P2001-192452A, P2002-322282A, JP-A-6-49209, JP-A-6-279589, and P2000-345044A to make the average particle size. 2 micron spherical siloxane.
- the spherical siloxane was heat-treated in an electric furnace at 350 degrees for 1 hour.
- the heat-treated spherical siloxane was subjected to a surface treatment by a dry method.
- the treatment agent was dimethyldimethoxysilane, and the sample was dried at 150 ° C for 3 hours after the treatment.
- the induction rate is less than 3, and the induction loss is less than 0.005, so that the 5G era filler has a low induction rate (small signal delay) and a low induction loss (less signal loss).
- methyltrimethoxysilane and tetraethoxysilane as raw materials, refer to the methods of Japanese Patent P2001-192452A, P2002-322282A, JP-A-6-49209, JP-A-6-279589, and P2000-345044A to make the average particle size. 2 micron spherical siloxane.
- the spherical siloxane was heat-treated in an electric furnace at 350 degrees for 1 hour.
- the heat-treated spherical siloxane is surface-treated by a dry method.
- the treating agents are dimethyldimethoxysilane (70% by weight) and hexamethyldisilazane (30% by weight).
- the temperature is 150 ° C for 3 hours after the treatment. An example sample was obtained by drying.
- Processing amount of mixed treatment agent (weight of mixed treatment agent / (weight of mixed treatment agent + weight of spherical siloxane)) ⁇ %.
- the sample obtained according to Example 13 has an inducement rate of less than 3 and an inducement loss of less than 0.005, so that the 5G era filler has a low inducement rate (small signal delay) and a low inducement loss (less signal loss).
- methyltrimethoxysilane and tetraethoxysilane as raw materials, refer to the methods of Japanese Patent P2001-192452A, P2002-322282A, JP-A-6-49209, JP-A-6-279589, and P2000-345044A to make the average particle size. 2 micron spherical siloxane.
- the spherical siloxane was heat-treated in an electric furnace at 350 degrees for 1 hour.
- the heat-treated spherical siloxane is subjected to a surface treatment by a dry method.
- the treating agents are vinyl dimethoxysilane (50% by weight) and hexamethyldisilazane (50% by weight), and dried at 150 ° C for 3 hours after treatment. Example samples were obtained.
- Processing amount of mixed treatment agent (weight of mixed treatment agent / (weight of mixed treatment agent + weight of spherical siloxane)) ⁇ %.
- the inducement rate is less than 3, and the inducement loss is less than 0.005, so that the 5G era filler has low inducement rate (small signal delay) and low inducement loss (small signal loss).
- methyltrimethoxysilane and tetraethoxysilane as raw materials, refer to the methods of Japanese Patent P2001-192452A, P2002-322282A, JP-A-6-49209, JP-A-6-279589, and P2000-345044A to make the average particle size. 2 micron spherical siloxane.
- the spherical siloxane was heat-treated in an electric furnace at 350 degrees for 1 hour.
- the heat-treated spherical siloxane was surface-treated by a dry method, and the treating agents were 3- (2,3-glycidoxypropyl) trimethoxysilane (30% by weight) and hexamethyldisilazane (70 % By weight) and dried at 150 ° C for 3 hours after treatment to obtain an example sample.
- Processing amount of mixed treatment agent (weight of mixed treatment agent / (weight of mixed treatment agent + weight of spherical siloxane)) ⁇ %.
- the induction rate is less than 3, and the induction loss is less than 0.005, so that the 5G era filler has a low induction rate (small signal delay) and low induction loss (less signal loss).
- the spherical siloxane was heat-treated in an electric furnace at 350 degrees for 1 hour.
- the heat-treated spherical siloxane was subjected to a surface treatment by a dry method, and the treatment agent was hexamethyldisilazane.
- the sample was dried at 150 ° C for 3 hours after the treatment.
- Hexamethyldisilazane treatment amount (weight of hexamethyldisilazane / (weight of hexamethyldisilazane + weight of spherical siloxane)) ⁇ %.
- the synthesis and determination results are listed in Table 8 below:
- the sample obtained according to Example 16 has an inducement rate of less than 3 and an inducement loss of less than 0.005, so that the 5G era filler has a low inducement rate (small signal delay) and a low inducement loss (less signal loss).
- methyltrimethoxysilane and tetraethoxysilane as raw materials, refer to the methods of Japanese Patent P2001-192452A, P2002-322282A, JP-A-6-49209, JP-A-6-279589, and P2000-345044A to make the average particle size. 2 micron spherical siloxane.
- the spherical siloxane was heat-treated in an electric furnace at 350 degrees for 1 hour.
- the heat-treated spherical siloxane was subjected to a surface treatment by a dry method.
- the treatment agent was dimethyldichlorosilane.
- the sample was dried at 150 ° C for 3 hours after the treatment.
- Amount of dimethyldichlorosilane treatment (weight of dimethyldichlorosilane / (weight of dimethyldichlorosilane + weight of spherical siloxane)) ⁇ %.
- Example 17 has an inducement rate of less than 3 and an inducement loss of less than 0.005, so that the 5G era filler has a low inducement rate (small signal delay) and a low inducement loss (small signal loss).
- methyltrimethoxysilane and tetraethoxysilane as raw materials, refer to the methods of Japanese Patent P2001-192452A, P2002-322282A, JP-A-6-49209, JP-A-6-279589, and P2000-345044A to make the average particle size. 2 micron spherical siloxane.
- the spherical siloxane was heat-treated in an electric furnace at 350 degrees for 1 hour.
- the heat-treated spherical siloxane was subjected to a surface treatment by a wet method.
- the treatment agent was dimethyldimethoxysilane, and the solvent was methyl ethyl ketone.
- the sample was dried at 150 ° C for 3 hours after the treatment.
- Amount of dimethyldimethoxysilane treatment (weight of dimethyldimethoxysilane / (weight of dimethyldimethoxysilane + weight of spherical siloxane)) ⁇ %.
- the electromotive force is less than 3 and the electromotive force loss is less than 0.005, so that the 5G era fillers have low electromotive force (small signal delay) and low electromotive force loss (less signal loss) Claim.
- sample obtained in the foregoing embodiments 1 to 18 may be subjected to a vertex cutting step to remove coarse particles.
- methods such as dry or wet sieving or inertial classification are used to remove 75, 55, 45, 20, 10, 5, 3, or 1 micron or more of the spherical powder filler according to the size of the semiconductor chip. Coarse particles.
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Abstract
Description
Claims (9)
- 一种球形粉体填料的制备方法,其特征在于,包括步骤:S1,提供组成为0-10wt%的Q单位和90-100wt%的T单位的球形硅氧烷;S2,对该球形硅氧烷进行热处理,以使得球形硅氧烷中的硅羟基发生缩合以得到缩合硅氧烷;以及S3,加入处理剂对缩合硅氧烷进行表面处理,以消除缩合硅氧烷中的硅羟基以得到球形粉体填料,该处理剂的重量百分比添加量为0.5-50wt%,该处理剂包括生成D单位和/或M单位的处理剂;其中,Q单位=SiO 4-;T单位=R 1SiO 3-、R 2SiO 3-、R 3SiO 3-、R 4SiO 3-和/或R 5SiO 3-;D单位=R a1R b1SiO 2-、R a2R b2Si 2O-和/或R a3R b3SiO 2-;M单位=R c1R d1R e1SiO-和/或R c2R d2R e2SiO-;其中的R 1,R 2,R 3,R 4,R 5选自由以下有机基组成的组中的至少一种:甲基,丙基,乙烯基,己基,苯基,长链烷基,环氧基,脂肪族氨基,芳香族氨基,甲基丙烯酰氧丙基,丙烯酰氧丙基,脲基丙基,氯丙基,巯基丙基,聚硫化物基,异氰酸酯丙基;其中的R a1,R b1,R a2,R b2,R a3,R b3,R c1,R d1,R e1,R c2,R d2,R e2选自由以下有机基组成的组中的至少一种:甲氧基,乙氧基,丙氧基,异丙氧基,氯基,硅氮烷。
- 根据权利要求1所述的制备方法,其特征在于,生成D单位的处理剂选自由以下处理剂组成的组中的至少一种:(CH 3) 2Si(OCH 3) 2,(CH 3) 2Si(OCH 2CH 3) 2,(CH 3)HSi(OCH 3) 2,(CH 3)HSi(OCH 2CH 3) 2,H 2Si(OCH 3) 2,H 2Si(OCH 2CH 3) 2,(C 6H 5) 2Si(OCH 3) 2,(C 6H 5) 2Si(OCH 2CH 3) 2,C 6H 5CH 3Si(OCH 3) 2,C 6H 5CH 3Si(OCH 2CH 3) 2,C 6H 5HSi(OCH 3) 2,C 6H 5HSi(OCH 2CH 3) 2。
- 根据权利要求1所述的制备方法,其特征在于,生成M单位的处理剂选自由以下处理剂组成的组中的至少一种:(CH 3) 3SiNHSi(CH 3) 3,(CH 3) 2C 6H 5SiNHSi(CH 3) 2C 6H 5,CH 3(C 6H 5) 2SiNHSiCH 3(C 6H 5)。
- 根据权利要求1所述的制备方法,其特征在于,处理剂还包括选自由以下偶联剂组成的组中的至少一种硅烷偶联剂:环氧基硅烷偶联剂,脂肪族氨基硅烷偶联剂,芳香族氨基硅烷偶联剂,甲基丙烯酰氧丙基硅烷偶联剂,丙烯酰氧丙基硅烷偶联剂,脲基丙基硅烷偶联剂,氯丙基硅烷偶联剂,巯基丙基硅烷偶联剂,聚硫化物基硅烷偶联剂,异氰酸酯丙基硅烷偶联剂。
- 根据权利要求1所述的制备方法,其特征在于,该制备方法包括使用 干法或湿法的筛分或惯性分级来除去球形粉体填料中的75微米以上的粗大颗粒。
- 根据权利要求1-5中任一项所述的制备方法得到的球形粉体填料,其特征在于,该球形粉体填料的粒径为0.1-50微米。
- 根据权利要求6所述的球形粉体填料,其特征在于,该球形粉体填料的诱电率为2.5-2.8,该球形粉体填料的诱电损失为0.0005-0.002,该球形粉体填料的热膨胀系数为5-15ppm。
- 根据权利要求6所述的球形粉体填料的应用,其特征在于,不同粒径的球形粉体填料紧密填充级配在树脂中形成复合材料。
- 根据权利要求8所述的应用,其特征在于,该复合材料适用于半导体封装材料、电路板及其中间半成品。
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US17/263,047 US20210309832A1 (en) | 2018-07-27 | 2018-07-27 | Method For Preparing Spherical Or Angular Powder Filler, Spherical Or Angular Powder Filler Obtained Therefrom, And Use Thereof |
CN201880090639.XA CN111868141A (zh) | 2018-07-27 | 2018-07-27 | 一种球形粉体填料的制备方法、由此得到的球形粉体填料及其应用 |
PCT/CN2018/099603 WO2020019372A1 (zh) | 2018-07-27 | 2018-08-09 | 一种球形粉体填料的制备方法、由此得到的球形粉体填料及其应用 |
CN201880090638.5A CN111867975A (zh) | 2018-07-27 | 2018-08-09 | 一种球形粉体填料的制备方法、由此得到的球形粉体填料及其应用 |
PCT/CN2019/075832 WO2020019709A1 (zh) | 2018-07-27 | 2019-02-22 | 一种球形或角形粉体填料的制备方法、由此得到的球形或角形粉体填料及其应用 |
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JP2021504462A JP7333099B2 (ja) | 2018-07-27 | 2019-02-22 | 球状又は角状粉末充填剤の調製方法、それから得られる球状又は角状粉末充填剤及びその用途 |
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