阅读说明：本技术 一种中空二氧化硅粉体填料的制备方法、由此得到的粉体填料及其应用 (Preparation method of hollow silica powder filler, powder filler obtained by preparation method and application of powder filler ) 是由 李文 莫忆凡 陈晨 于 2021-01-29 设计创作，主要内容包括：本发明涉及一种中空二氧化硅粉体填料的制备方法,其包括将纳米尺寸的前驱体分散于含水液体中得到含前驱体的分散液,将R-1SiX-3硅烷加入分散液中,其中,R-1SiX-3硅烷与分散液中的水进行水解缩合反应来提供包括T单位的聚硅氧烷,得到包括前驱体和聚硅氧烷的混合物,前驱体为可溶解于酸的前驱体且其粒径小于聚硅氧烷的粒径；在混合物中加酸以溶解前驱体,得到聚硅氧烷粉体；在含氧氛围中煅烧聚硅氧烷粉体,煅烧温度介于850度-1200度之间,得到中空二氧化硅粉体填料。本发明还涉及由此得到的粉体填料及其应用。本发明的粉体填料通过在二氧化硅内部导入气孔以降低介电损失和介电常数。(The invention relates to a preparation method of hollow silicon dioxide powder filler, which comprises the steps of dispersing a precursor with a nano size in aqueous liquid to obtain dispersion liquid containing the precursor, and adding R 1 SiX 3 Adding silane into the dispersion, wherein R 1 SiX 3 Carrying out hydrolysis condensation reaction on silane and water in the dispersion liquid to provide polysiloxane containing T units, and obtaining a mixture containing a precursor and the polysiloxane, wherein the precursor is a precursor capable of being dissolved in acid, and the particle size of the precursor is smaller than that of the polysiloxane; adding acid into the mixture to dissolve the precursor to obtain polysiloxane powder; and (3) calcining the polysiloxane powder in an oxygen-containing atmosphere at the calcining temperature of 850-1200 ℃ to obtain the hollow silica powder filler. The invention also relates to the powder thus obtainedA filler and its use. The powder filler of the present invention reduces dielectric loss and dielectric constant by introducing pores into the silica.)

1. The preparation method of the hollow silica powder filler is characterized by comprising the following steps:

s1, dispersing the precursor with nanometer size in the water-containing liquid to obtain the dispersion liquid containing the precursor, and R₁SiX₃Adding silane into the dispersion, wherein R₁SiX₃Performing hydrolytic condensation reaction on silane and water in the dispersion liquid to provide polysiloxane containing T units, and obtaining a mixture containing a precursor and the polysiloxane, wherein the precursor is a precursor capable of dissolving in acid and has a particle size smaller than that of the polysiloxane, and R is₁Is a hydrogen atom or an independently selected organic group of carbon atoms 1 to 18, X is a water-decomposable group, and T has the unit of R₁SiO₃-；

S2, adding acid into the mixture to dissolve the precursor to obtain polysiloxane powder;

and S3, calcining the polysiloxane powder in an oxygen-containing atmosphere at the calcining temperature of 850-1200 ℃ to obtain the hollow silica powder filler.

2. The method of claim 1, wherein the volume fraction of the precursor in the mixture is between 10% and 60%.

3. The method according to claim 1, wherein the particle size of the precursor is less than or equal to one third of the particle size of the polysiloxane.

4. The method according to claim 1, wherein the polysiloxane further comprises Q units, D units, and/or M units, wherein Q units are SiO units₄-, D unit ═ R₂R₃SiO₂-, M units ═ R₄R₅R₆SiO₂-，R₂，R₃，R₄，R₅，R₆Each hydrogen atom or an independently selected organic group of carbon atoms 1 to 18.

5. The process according to claim 4, wherein the T unit of the polysiloxane is the raw material R₁SiX₃At least one selected from the group consisting of methyltrimethoxysilane, hydrocarbyl trihydrocarbyloxysilane, methyltrichlorosilane and hydrocarbyl trichlorosilane, Q is a unit selected from at least one selected from the group consisting of tetrahydrocarbyloxysilane, silicon tetrachloride and silicon dioxide, D is a unit selected from at least one selected from the group consisting of dihydrocarbyldihydrocarbyloxysilane and dihydrocarbyldichlorosilane, and M is a unit selected from at least one selected from the group consisting of trihydrocarbylalkoxysilane, trihydrocarbylchlorosilane and hexahydrocarbyldisilazane.

6. The preparation method of claim 1, further comprising adding a treating agent to perform surface treatment on the hollow silica powder filler, wherein the treating agent comprises a silane coupling agent and/or disilazane; the silane coupling agent is (R)₇)_a(R₈)_bSi(M)_4-a-b，R₇，R₈Is an independently selected hydrocarbon group of carbon atoms 1 to 18, a hydrogen atom, or a substituted hydrocarbon groupA hydrocarbon group of carbon atoms 1 to 18 substituted with a functional group selected from at least one of the following organic functional groups: vinyl, allyl, styryl, epoxy, aliphatic amino, aromatic amino, methacryloxypropyl, acryloxypropyl, ureidopropyl, chloropropyl, mercaptopropyl, polysulfide, isocyanatopropyl; m is a hydrocarbyloxy group of carbon atoms 1 to 18 or a halogen atom, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, a + b is 1, 2 or 3; the disilazane is (R)₉R₁₀R₁₁)SiNHSi(R₁₂R₁₃R₁₄)，R₉，R₁₀，R₁₁，R₁₂，R₁₃，R₁₄Is an independently selected hydrocarbon group of carbon atoms 1 to 18 or a hydrogen atom.

7. The powder filler obtained by the preparation method according to any one of claims 1 to 6, wherein the powder filler has a specific gravity of less than or equal to 2.15 and an average particle size of 0.5 to 50 micrometers.

8. The use of powder filler according to claim 7, wherein the hollow silica powder filler of different particle sizes is tightly packed and graded in resin to form a composite material suitable for circuit board materials and semiconductor packaging materials.

9. The use according to claim 8, wherein the hollow silica powder filler is a hollow spherical silica powder filler or a hollow angular silica powder filler.

10. The use of claim 8, further comprising removing coarse large particles of 1 micron, 3 microns, 5 microns, 10 microns, 20 microns or more from the hollow silica powder filler using dry or wet sieving or inertial classification.

Technical Field

The invention relates to a circuit board and a semiconductor packaging material, in particular to a preparation method of a hollow silica powder filler, the powder filler obtained by the preparation method and application of the powder filler.

Background

In the field of 5G communication, radio frequency devices and the like are required to be used for assembling equipment, High Density Interconnect (HDI) boards, high frequency high speed boards, mother boards and other circuit boards and semiconductor packaging materials. These circuit boards and semiconductor sealing materials are generally composed mainly of an organic polymer such as epoxy resin, aromatic polyether, fluorine resin, etc., and a filler, and the filler has a main function of reducing the thermal expansion coefficient of the organic polymer. The existing filler is selected from spherical or angular silica for tight filling grading.

With the advance of technology, the signal frequencies used for semiconductors are becoming higher, and the high speed and low loss of signal transmission speed require fillers for circuit board (substrate) materials or semiconductor (chip) packaging materials to have low dielectric loss and permittivity. The dielectric constant of the material is basically determined by the chemical composition and structure of the material, and the spherical or angular silicon dioxide has the inherent dielectric constant, so that the dielectric loss and the dielectric constant of the spherical or angular silicon dioxide prepared by the existing method cannot be further reduced.

Disclosure of Invention

In order to solve the problem that the dielectric loss and the dielectric constant of the silicon dioxide in the prior art cannot be further reduced, the invention provides a preparation method of a hollow silicon dioxide powder filler, the powder filler obtained by the preparation method and application of the powder filler.

The preparation method of the hollow silica powder filler comprises the following steps: s1, dispersing the precursor with nanometer size in the water-containing liquid to obtain the dispersion liquid containing the precursor, and R₁SiX₃Adding silane into the dispersion, wherein R₁SiX₃Performing hydrolytic condensation reaction on silane and water in the dispersion liquid to provide polysiloxane containing T units, and obtaining a mixture containing a precursor and the polysiloxane, wherein the precursor is a precursor capable of dissolving in acid and has a particle size smaller than that of the polysiloxane, and R is₁Is a hydrogen atom or an independently selected organic group of carbon atoms 1 to 18, X is a water-decomposable group, and T has the unit of R₁SiO₃-; s2, adding acid into the mixture to dissolve the precursor to obtain polysiloxane powder; and S3, calcining the polysiloxane powder in an oxygen-containing atmosphere at the calcining temperature of 850-1200 ℃ to obtain the hollow silica powder filler.

Preferably, the precursor is substantially insoluble in water in alkaline or neutral water, and soluble in water under acidic conditions. The term "substantially insoluble in water" as used herein means that the solubility in water at room temperature is 1% or less. The present application has no particular requirement for the precursor as long as the above conditions are satisfied. More preferably, the precursor is a weak acid salt, carbonate, basic carbonate, acid carbonate, organic acid salt, hydroxide, and/or oxide of the metal. In preferred embodiments, the precursor is an alkaline earth or transition metal carbonate, an alkaline earth or transition metal oxalate, magnesium hydroxide, aluminum hydroxide, zinc oxide, or the like.

Preferably, the acid that dissolves the precursor is hydrochloric acid, sulfuric acid and/or nitric acid.

Preferably, the volume fraction of the precursor in the mixture is between 10% and 60%.

Preferably, the particle size of the precursor is less than one third of the particle size of the polysiloxane. In a preferred embodiment, the particle size of the precursor is in the range of 100nm to 500 nm.

Preferably, the aqueous liquid in step S1 is a liquid containing water as a main component. In particular, the volume ratio of water in the aqueous liquid is greater than 80%. More preferably, the water in the aqueous liquid is reacted with R₁SiX₃The weight ratio of the silane is between 600 and 1500: 80.

Preferably, X is a hydrocarbyloxy group or a halogen atom.

Preferably, the precursor in step S1 is encapsulated in polysiloxane. It is to be understood that the method of coating the precursor with the polysiloxane is not particularly limited. The precursor can be effectively coated by dispersing the precursor in water and then synthesizing polysiloxane in water.

Preferably, the polysiloxane further comprises Q units, D units, and/or M units, wherein Q units ═ SiO units₄-, D unit ═ R₂R₃SiO₂-, M units ═ R₄R₅R₆SiO₂-，R₂，R₃，R₄，R₅，R₆Each hydrogen atom or an independently selected organic group of carbon atoms 1 to 18.

Preferably, T units of the polysiloxane as starting material R₁SiX₃At least one selected from the group consisting of methyltrimethoxysilane, hydrocarbyl trihydrocarbyloxysilane, methyltrichlorosilane and hydrocarbyl trichlorosilane, Q is a unit selected from at least one selected from the group consisting of tetrahydrocarbyloxysilane, silicon tetrachloride and silicon dioxide, D is a unit selected from at least one selected from the group consisting of dihydrocarbyldihydrocarbyloxysilane and dihydrocarbyldichlorosilane, and M is a unit selected from at least one selected from the group consisting of trihydrocarbylalkoxysilane, trihydrocarbylchlorosilane and hexahydrocarbyldisilazane. In a preferred embodiment, the polysiloxane is prepared from at least one of methyltrimethoxysilane, tetraethoxysilane, dimethyldimethoxysilane and propyltrimethoxysilane.

Preferably, the calcination temperature is between 850 degrees and 1100 degrees and the calcination time is between 6 hours and 12 hours. In a preferred embodiment, the calcination temperature is 950 to 1050 degrees.

Preferably, the preparation method further comprises the step of adding a treating agent to carry out surface treatment on the hollow silica powder filler, wherein the treating agent comprises a silane coupling agent and/or disilazane; the silane coupling agent is (R)₇)_a(R₈)_bSi(M)_4-a-b，R₇，R₈Is an independently selectable hydrocarbon group of carbon atoms 1 to 18, a hydrogen atom, or a hydrocarbon group of carbon atoms 1 to 18 substituted with a functional group selected from at least one of the following organofunctional groups: vinyl, allyl, styryl, epoxy, aliphatic amino, aromatic amino, methacryloxypropyl, acryloxypropyl, ureidopropyl, chloropropyl, mercaptopropyl, polysulfide, isocyanatopropyl; m is a hydrocarbyloxy group of carbon atoms 1 to 18 or a halogen atom, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, a + b is 1, 2 or 3; the disilazane is (R)₉R₁₀R₁₁)SiNHSi(R₁₂R₁₃R₁₄)，R₉，R₁₀，R₁₁，R₁₂，R₁₃，R₁₄Is an independently selected hydrocarbon group of carbon atoms 1 to 18 or a hydrogen atom.

The invention also provides the powder filler obtained by the preparation method, wherein the specific gravity of the powder filler is less than or equal to 2.15, and the average particle size is between 0.5 and 50 micrometers. In a preferred embodiment, the powder filler has a specific gravity of between 0.72 and 1.7 and an average particle size of between 0.7 microns and 4.8 microns.

The invention also provides the application of the powder filler, wherein the hollow silica powder filler with different particle sizes is tightly filled and graded in resin to form a composite material which is suitable for circuit board materials and semiconductor packaging materials.

Preferably, the hollow silica powder filler is a hollow spherical silica powder filler or a hollow angular silica powder filler. More preferably, the hollow silica powder filler is a hollow spherical silica powder filler to increase the filling amount of the hollow silica powder filler in the resin.

Preferably, the application further comprises removing coarse large particles of 1 micron, 3 microns, 5 microns, 10 microns, 20 microns or more in the hollow silica powder filler using dry or wet sieving or inertial classification.

According to the preparation method of the hollow silica powder filler, the precursor capable of dissolving in acid is coated in polysiloxane, and then the polysiloxane is oxidized into silica in the oxygen-containing atmosphere to successfully prepare the hollow silica powder.

Detailed Description

The following provides a detailed description of the preferred embodiments of the present invention.

The detection methods referred to in the following examples include:

the average particle size is measured by a laser particle size distribution instrument LA-700 of HORIBA;

the volume fraction of the precursor in the mixture (precursor weight/precursor specific gravity)/(precursor weight/specific gravity of precursor + weight of polysiloxane/specific gravity of polysiloxane), wherein the specific gravity of the polymethylsiloxane is 1.34;

measuring the specific gravity of the powder by using a helium gas specific gravity meter;

herein, "degree" refers to "degrees celsius," i.e., the temperature of the sample;

herein, the average particle diameter refers to the volume average diameter of the particles.

Example 1

Taking a certain weight part of deionized water containing a certain amount of 100nm calcium carbonate in the water at room temperature, putting the deionized water into a reaction kettle with a stirrer, starting stirring, adding 80 weight parts of methyltrimethoxysilane, and stirring for 1 hour. After the methyltrimethoxysilane was dissolved, 25 parts by weight of 5% ammonia water was added thereto, and the stirring was stopped after 10 seconds, to obtain a mixture comprising the precursor and the polysiloxane. Standing for 1 hour, adding dilute nitric acid into water to dissolve calcium carbonate, filtering, and drying to obtain spherical powder. And (3) slowly heating the powder in a muffle furnace, discharging organic matters in an oxygen-containing atmosphere, heating to 1050 ℃, and calcining for 12 hours to obtain the spherical hollow silica powder. The results of the analysis of the samples are shown in Table 1 below.

TABLE 1

Example 2

Taking a certain weight part of deionized water at room temperature, putting a certain amount of zinc oxide particles with the average particle size of 250 nanometers into a reaction kettle with a stirrer, starting stirring, adding 80 weight parts of methyltrimethoxysilane, and stirring for 1 hour. After the methyltrimethoxysilane was dissolved, 25 parts by weight of 5% ammonia water was added thereto, and the stirring was stopped after 10 seconds, to obtain a mixture comprising the precursor and the polysiloxane. Standing for 1 hour, adding nitric acid into water to dissolve zinc oxide, filtering, and drying to obtain spherical powder. And (3) putting the powder into a muffle furnace, slowly heating the powder, discharging organic matters in an oxygen-containing atmosphere, heating the powder to 850 ℃, and calcining the powder for 12 hours to obtain the spherical hollow silica powder. The results of the analysis of the samples are shown in Table 2 below.

TABLE 2

Example 3

Taking a certain weight part of deionized water containing a certain amount of calcium carbonate with the average particle size of 500 nanometers at room temperature, putting the deionized water into a reaction kettle with a stirrer, starting stirring, adding 80 weight parts of methyltrimethoxysilane, and stirring for 1 hour. The volume fraction of calcium carbonate was 30%. Adding nitric acid into water to dissolve calcium carbonate, filtering, washing with water, and drying. The white solid was pulverized by a pulverizer to obtain angular powder having an average particle diameter of 50 μm. The agglomerated powder was put into a muffle furnace and slowly heated to an oxygen-containing atmosphere to discharge the organic matter and heated to 1000 ℃ and calcined for 12 hours to obtain the angular hollow silica powder of example 8. The sample had an average particle size of 42 microns and a specific gravity of 1.20.

Example 4

Taking a certain weight part of deionized water at room temperature, putting a certain amount of magnesium hydroxide particles with the average particle size of 250 nanometers into a reaction kettle with a stirrer, starting stirring, adding 75 weight parts of methyltrimethoxysilane and 5 weight parts of tetraethoxysilane, and stirring for 1 hour. After methyltrimethoxysilane and tetraethoxysilane were dissolved, 25 parts by weight of 5% ammonia water was added thereto, and stirring was stopped after 10 seconds to obtain a mixture comprising the precursor and polysiloxane. Standing for 1 hour, adding nitric acid into water to dissolve magnesium hydroxide, filtering, and drying to obtain spherical powder. And putting the powder into a muffle furnace, slowly heating the powder, discharging organic matters in an oxygen-containing atmosphere, heating the powder to 1000 ℃, and calcining the powder for 12 hours to obtain the spherical hollow silica powder. The results of the analysis of the samples are shown in Table 3 below.

TABLE 3

Example 5

Taking a certain weight part of deionized water containing a certain amount of aluminum hydroxide particles with the average particle size of 250 nanometers at room temperature, putting the deionized water into a reaction kettle with a stirrer, starting stirring, adding 78 weight parts of methyltrimethoxysilane and 2 weight parts of dimethyldimethoxysilane, and stirring for 1 hour. After methyltrimethoxysilane and dimethyldimethoxysilane were dissolved, 25 parts by weight of 5% ammonia water was added thereto, and stirring was stopped after 10 seconds to obtain a mixture comprising the precursor and polysiloxane. After standing for 1 hour, adding nitric acid into water to dissolve aluminum hydroxide, filtering, and drying to obtain spherical powder. And putting the powder into a muffle furnace, slowly heating the powder, discharging organic matters in an oxygen-containing atmosphere, heating the powder to 950 ℃, and calcining the powder for 12 hours to obtain the spherical hollow silica powder. The results of the analysis of the samples are shown in Table 4 below.

TABLE 4

Example 6

Taking a certain weight part of deionized water at room temperature, putting the deionized water containing a certain amount of calcium oxalate particles with the average particle size of 250 nanometers into a reaction kettle with a stirrer, starting stirring, adding 78 weight parts of methyltrimethoxysilane and 2 weight parts of propyltrimethoxysilane, and stirring for 1 hour. After the methyltrimethoxysilane and the propyltrimethoxysilane were dissolved, 25 parts by weight of 5% ammonia water was added, and stirring was stopped after 10 seconds, to obtain a mixture including the precursor and the polysiloxane. Standing for 1 hour, adding nitric acid into water to dissolve calcium oxalate, filtering, and drying to obtain spherical powder. And putting the powder into a muffle furnace, slowly heating the powder, discharging organic matters in an oxygen-containing atmosphere, heating the powder to 950 ℃, and calcining the powder for 12 hours to obtain the spherical hollow silica powder. The results of the analysis of the samples are shown in Table 5 below.

TABLE 5

It is to be understood that the example samples obtained in examples 1 to 11 described above may be surface-treated. Specifically, treatments such as a vinyl silane coupling agent, epoxy silane coupling, disilazane, and the like may be performed as necessary. More than one treatment may be performed as necessary.

It is to be understood that the preparation method includes the use of dry or wet screening or inertial classification to remove coarse large particles above 1, 3, 5, 10, 20 microns in the filler.

It should be understood that the closely packed grading of spherical silica fillers of different particle sizes forms a composite in the resin.

The above embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and various changes may be made in the above embodiments of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.