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WO2023208006A1 - Dispersion de résine de particules de nano-silice modifiées et procédé de préparation et application de dispersion de résine - Google Patents

Dispersion de résine de particules de nano-silice modifiées et procédé de préparation et application de dispersion de résine Download PDF

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Publication number
WO2023208006A1
WO2023208006A1 PCT/CN2023/090707 CN2023090707W WO2023208006A1 WO 2023208006 A1 WO2023208006 A1 WO 2023208006A1 CN 2023090707 W CN2023090707 W CN 2023090707W WO 2023208006 A1 WO2023208006 A1 WO 2023208006A1
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Prior art keywords
modified
resin
resin dispersion
dispersion
particles
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English (en)
Chinese (zh)
Inventor
袁灿
盛吕红
解孝林
刘成杰
包旭升
周兴平
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Huawei Technologies Co Ltd
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Huawei Technologies Co Ltd
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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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
    • C08K5/1575—Six-membered rings
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present application relates to the field of semiconductor packaging technology, and specifically to a resin dispersion of modified nanosilica particles and its preparation method and application.
  • Resin such as epoxy resin
  • Silica is usually added to it, mostly micron-grade silica.
  • nanoscale silicon dioxide with better anti-settlement ability and narrow gap filling ability.
  • Nano-silica powder has a high surface energy and is easy to agglomerate. Adding it to the encapsulating resin in the form of a resin dispersion can help reduce its agglomeration before use. However, nano-silica particles are not related to dispersion. The compatibility of the resin is not high and it is easy to agglomerate, which will reduce the fluidity of the packaging material and affect the packaging quality. At the same time, it is difficult to increase the solid content of the resin dispersion, which will not effectively reduce the thermal expansion coefficient of the packaging material.
  • embodiments of the present application provide a resin dispersion of modified nanosilica that can be directly used in the field of semiconductor packaging to improve packaging reliability.
  • the first aspect of the embodiment of the present application provides a resin dispersion liquid, which includes modified nano-silica particles, a dispersion resin and a co-dispersing agent, wherein the modified nano-silica particles are nano-silica particles surface-modified with silane.
  • Silica the mass percentage of the modified nano-silica particles in the resin dispersion is 39-60 wt%, based on the average value of the modified nano-silica particles measured by the dynamic light scattering method
  • the ratio of the particle size to its average primary particle size is less than or equal to 2.0.
  • the mass proportion of modified nanosilica particles in the above-mentioned resin dispersion is relatively high, and the ratio of its average dispersed particle size to its average primary particle size is less than or equal to 2.0, reflecting the better monodispersity of the particles in the resin dispersion.
  • the modified nano-silica particles can be evenly dispersed in it, without significantly reducing the fluidity of the encapsulating material, and can effectively increase the filling amount of particles and reduce the thermal expansion of the encapsulating material. coefficient.
  • the true density of the modified nanosilica particles is 2.0-2.2g/cm 3 .
  • This true density breaks through the limitation of the true density of SiO 2 particles produced by conventional alkoxysilane hydrolysis method (generally below 1.8g/cm 3 ). There is no need to calcination and other treatments to achieve densification of the particles, and it is During the mixing process with resin materials, it can withstand high-speed shear force without causing damage or affecting the thixotropy of the mixed material.
  • the resin dispersion does not contain organic amines.
  • organic amines are not used when preparing SiO 2 particles, and organic amines are not needed to stabilize the resin dispersion. However, it can still ensure that the true density of the modified nanosilica particles is high and the particle size distribution is narrow.
  • the resin dispersion does not contain organic amines, when the resin dispersion is combined with chemicals that are not resistant to When epoxy resin, the encapsulating raw material of organic amine, is mixed, it will not affect the storage stability of the resulting mixed material and the thermal/mechanical properties of the cured product.
  • the particle size variation coefficient of the modified nanosilica particles based on transmission electron micrographs is less than or equal to 15%.
  • the modified nanosilica particles have a narrow particle size distribution and are not easy to settle in the resin medium.
  • the resin dispersion has high storage stability and appropriate viscosity. When the resin dispersion is added to the resin material, higher The filling rate has a more obvious effect on reducing the thermal expansion coefficient of the cured product of the overall material.
  • the total content of metal ion impurities in the resin dispersion is less than 10 ppm, the content of single metal ion impurities is less than 3 ppm, and the content of halogen ions is less than 3 ppm.
  • the resin dispersion has low impurity ion content and is particularly suitable for use in the field of semiconductor packaging that requires high purity of raw materials. It can greatly reduce corrosion of electronic components and metal circuits and ensure the reliability of the package.
  • the second aspect of the embodiment of the present application provides a resin dispersion liquid, which includes modified nano-silica particles, a dispersing resin and a co-dispersing agent, wherein the modified nano-silica particles are nano-silica particles surface-modified with silane.
  • Silica the true density of the modified nano-silica particles is 2.0-2.2g/cm 3 ; the total content of metal ion impurities in the resin dispersion is less than 10ppm, the content of single metal ion impurities is less than 3ppm, halogen The content of ions is less than 3ppm.
  • the true density of the modified nano-silica particles contained in the above-mentioned resin dispersion can be as high as 2.0-2.2g/cm 3 , breaking through the limit on the true density of SiO 2 particles produced by the conventional alkoxy silicon hydrolysis method, without the need for
  • the particles are then subjected to calcination and other treatments to achieve densification, and during the mixing process with the resin material, they can withstand high-speed shear force without being damaged or affecting the thixotropy of the mixed material.
  • the impurity content in the resin dispersion is low, and there is no problem of high impurity content caused by the water glass preparation method. It is especially suitable for use in the field of semiconductor packaging that requires high material purity, and can greatly reduce the impact on electronic components and Metal lines cause corrosion to improve reliability.
  • the third aspect of the embodiment of the present application also provides a modified silica sol, which contains modified nano-silica particles, wherein the modified nano-silica particles are nano-silica surface-modified with an organic silicon compound , the true density of the modified nanosilica particles is 2.0-2.2g/cm 3 ; the total content of metal ion impurities in the modified silica sol is less than 10ppm, the content of single metal ion impurities is less than 3ppm, and the content of halogen ions is The content is less than 3ppm.
  • the particle size variation coefficient of the modified nanosilica particles based on transmission electron micrographs is less than or equal to 15%.
  • the fourth aspect of the embodiments of the present application also provides a preparation method of modified silica sol, which includes the following steps:
  • silicon sources containing alkali metal and chlorine impurities such as alkali metal silicates and chlorine-containing silanes are not used. Instead, silicon alkoxide is used as the silicon source.
  • silicon alkoxide is used as the silicon source.
  • the fifth aspect of the embodiment of the present application also provides a method for preparing a resin dispersion, which includes the following steps:
  • the above preparation method is suitable for preparing the resin dispersion as described in the first aspect or the second aspect of the present application.
  • silicon alkoxide is used as the silicon source.
  • the speed of the stirring reaction is controlled within a certain range, so that the nucleation speed of SiO 2 particles and The growth rate is controlled within an appropriate range, and nano-sized SiO 2 particles with low particle size variation coefficient, high true density, and low impurity content can be obtained, and then the surface modification of the modifier and the co-dispersant are used to replace the SiO 2 particles in the silica sol.
  • the reaction medium can also ensure that the obtained resin dispersion has excellent particle dispersion performance and high solid content.
  • the sixth aspect of the embodiment of the present application also provides a resin composition, which includes a host resin material and the resin dispersion liquid mentioned above in the embodiment of the present application.
  • the seventh aspect of the embodiment of the present application provides a cured product, which is obtained by curing the resin composition described in the fifth aspect of the present application.
  • the eighth aspect of the embodiment of the present application provides a semiconductor package, which includes the cured product described in the seventh aspect of the present application.
  • FIG. 1 is a schematic structural diagram of a semiconductor package according to an embodiment of the present application.
  • Figure 2 is a transmission electron microscope (TEM) photo of the resin dispersion of modified nanosilica particles provided in Example 1.
  • Figure 3 is a particle size distribution diagram of the resin dispersion of Example 1 measured based on the dynamic light scattering method.
  • Figure 4 is a section scanning electron microscope photograph of the cured product of the epoxy resin composition provided in Example 1.
  • Figure 5 is a transmission electron microscope photograph of the resin dispersion of modified nanosilica particles provided in Example 2.
  • Figure 6 is a particle size distribution diagram of the resin dispersion of Example 2 measured based on the dynamic light scattering method.
  • FIG. 1 is a schematic structural diagram of a semiconductor package provided by an embodiment of the present application.
  • the semiconductor package 100 includes a substrate 10 , an electronic component 20 disposed on one side surface of the substrate 10 , and a plastic package 30 that encapsulates the substrate 10 and the electronic component 20 .
  • the electronic components may be one or more of chips, transistors (such as diodes, transistors), LEDs, resistor-capacitor components (such as resistors, capacitors, inductors), etc.
  • the electronic component 20 is a chip as an example for description.
  • the surface of the chip 20 facing the substrate 10 may have a plurality of solder bumps 201 , and the chip 20 may be attached to the surface of the substrate 10 by remelting the solder bumps 201 .
  • an underfill glue layer 202 is also provided in the gap between the solder bumps 201 to fill the gap between the chip 20 and the substrate 10 to provide a more stable connection.
  • At least one of the above-mentioned plastic encapsulation body 30 and the underfill glue layer 202 can be cured by a resin composition containing epoxy resin and filler.
  • Adding fillers is mainly based on the fact that the cured product of simple epoxy resin has a high coefficient of thermal expansion (CTE), which can easily cause the plastic package 30 and the bottom filling layer 202 to warp and reduce reliability. The addition of fillers can improve This question.
  • the filler suitable for the plastic package 30 and the bottom filling glue layer 202 can be silica whose thermal expansion coefficient is much lower than that of the resin; in addition, in order to ensure that the CTE of the plastic package 30 and the bottom filling glue layer 202 can be effectively reduced, the silicon dioxide
  • the mass proportion of silicon filler ie, filling rate
  • adding nanoscale silica filler in the form of a resin dispersion to a resin composition containing a host resin such as epoxy resin
  • a host resin such as epoxy resin
  • silica resin dispersions cannot take into account these two characteristics.
  • the embodiments of the present application provide a resin dispersion of silica, wherein the resin dispersion includes modified nano-silica particles, a dispersing resin and a co-dispersing agent, wherein the modified nano-silica particles are organic Nano-silica modified with silicon compound surface, the mass percentage of modified nano-silica particles in the resin dispersion is 39-60 wt%, the modified nano-silica particles measured based on dynamic light scattering method The ratio of the average particle size to its average primary particle size is less than or equal to 2.0.
  • the average primary particle size of the above-mentioned modified nano-silica particles can be recorded as D1, based on the dry modified nano-silica particles (ie, the medium obtained after removing the dispersion resin and co-dispersant in the resin dispersion).
  • the average particle size of the modified nanosilica particles in the resin dispersion measured based on the dynamic light scattering method (DLS method) is recorded as D2 (unit is nm), and the D2 can also be called “ D50 particle size” essentially reflects the average diameter of secondary particles of silica material in the dispersion medium.
  • D2/D1 can reflect the degree of dispersion of modified nano-silica particles in the form of single particles. The smaller the ratio, the better the degree of dispersion of modified nano-silica particles in the resin dispersion and the less particle aggregation. In the resin dispersion of silica of the present application, D2/D1 ⁇ 2 can be achieved, which indicates that the monodispersity of the modified nano-silica particles is better.
  • the resin dispersion is added to systems such as semiconductor encapsulation resin materials. It is well compatible with the encapsulating resin and can be evenly dispersed in it. It will not significantly affect the rheological properties of the encapsulating material, reduce its fluidity, reduce its transparency, increase its viscosity, etc.
  • the modified nano-silica particles have better dispersion in the resin dispersion and have a high mass ratio. It can be in the range of 39-60wt%.
  • the resin dispersion is added to the encapsulating material formula, such as a resin composition containing encapsulating host resin, the filling rate of silica in the encapsulating material is correspondingly higher. This can effectively reduce the thermal expansion coefficient of the packaging material. Therefore, the resin dispersion of the present application can ensure a high content of modified nano-silica particles and at the same time ensure excellent dispersibility.
  • the mass percentage of modified nanosilica particles in the resin dispersion can be 48-60 wt%, such as 50%, 52%, 55%, 60%, etc.
  • the content of modified nano-silica particles in the resin dispersion is higher, and under the synergistic effect of dispersants and surface modifiers, the silica particles can still maintain good dispersion.
  • the mass percentage of the dispersing agent in the above-mentioned resin dispersion is 0.3-10wt%, and the mass percentage of the dispersing resin in the above-mentioned resin dispersion is 30-60wt%.
  • Dispersion resin is the main dispersion medium of resin dispersion. The presence of appropriate amount of co-dispersant can improve the dispersion of modified nano-silica particles in resin dispersion and increase its mass proportion.
  • the dispersing aid includes one or more of ether substances, ketone substances, ester substances, amide substances, and nitrile substances.
  • the presence of co-dispersants can improve the dispersion of modified nano-silica particles in the resin dispersion.
  • some wetting and dispersing agents can improve the dispersion of nano-silica particles in the resin dispersion. dispersion and storage stability.
  • ether substances may include but are not limited to ethylene glycol methyl ether, Tetrahydrofuran, dioxane, diethyl ether, dibutyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutyl One or more of oxyethane, modified polyether wetting and dispersing agents, etc.; ketones can include but are not limited to acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl One or more of isobutyl ketone, 2-heptanone, diisobutyl ketone, cyclohexanone,
  • the dispersion resin includes at least one of epoxy resin, phenolic resin, acrylic resin, polysiloxane, polyamic acid, and polyurethane monomers or prepolymers.
  • the dispersion resin is a monomer of these resins, so as to have better dilution ability and facilitate the dispersion of silica particles therein.
  • the average particle size of the modified nanosilica particles measured based on the dynamic light scattering method is in the range of 15nm-150nm. That is, the above-mentioned D2 is 15nm-150nm. In some embodiments, D2 is 15nm-100nm; in other embodiments, D2 is 18nm-80nm; in yet other embodiments, D2 is 18-50nm.
  • the true density of the modified nanosilica particles is 2.0-2.2g/cm 3 .
  • the true density of the modified nanosilica particles is within the above range, breaking through the limitation of the low true density (generally below 1.8g/ cm3 ) of SiO2 particles produced by the conventional alkoxy silicon hydrolysis method.
  • Higher The true density can achieve densification without the need for calcination and other treatments, and ensures that it can withstand high-speed shear force without damage during the mixing process with the encapsulating resin material, and does not affect the thixotropy of the resin composition, which is particularly suitable For application scenarios requiring high mechanical properties.
  • the true density can be measured using a gas displacement true density meter (such as AccuPyc II 1340 instrument from Micromeritics Company). Specifically, the dry powder sample of modified nanosilica particles is loaded into the sample holder and then filled. Replacement gas (such as helium), the true density of the sample is calculated based on the filling amount of the replacement gas and the weight of the sample.
  • a gas displacement true density meter such as AccuPyc II 1340 instrument from Micromeritics Company.
  • the resin dispersion does not contain organic amines.
  • Organic amines are usually introduced in the process of preparing SiO 2 particles using alkoxy silicon hydrolysis to improve their true density and stability of SiO 2 sol.
  • Organic amines also exist in SiO 2 sol and resin dispersion. Commonly used organic amines include primary amines, secondary amines, tertiary amines or quaternary amines. In this application, no organic amine is used when preparing SiO 2 particles, and the corresponding resin dispersion does not contain organic amines. At this time, the true density of the modified nanosilica particles can also be guaranteed to be high and the particle size distribution Also narrower.
  • the resin dispersion does not contain organic amines
  • the organic amine may participate in the cross-linking reaction of the epoxy resin, affecting the storage of the liquid mixture. Stability and thermal/mechanical properties of cured products affect quality reliability.
  • the resin dispersion does not contain organic amines is not limited to the content of organic amines being 0.
  • the content of organic amines in the resin dispersion is ⁇ 0.9 ⁇ mol/g. , it can also be regarded as free of organic amines.
  • the particle size variation coefficient of the modified nanosilica particles obtained based on transmission electron micrographs is less than or equal to 15%.
  • the particle size of the modified nanosilica particles known based on transmission electron microscope (TEM) photos can be called the TEM particle size.
  • the coefficient of variation of the TEM particle size specifically refers to the TEM particle size.
  • Relative standard deviation i.e., the standard deviation ⁇ divided by the arithmetic mean of multiple TEM particle sizes.
  • the TEM particle size can be observed at a certain magnification of TEM photos of modified nanosilica particles, and the diameters of at least 200 particles in a TEM photo are measured, and the standard deviation of the diameters of multiple particles is calculated based on this. and arithmetic mean, and then obtain the particle size variation coefficient.
  • the above particle size variation coefficient is ⁇ 15%, which can reflect that the particle size distribution of modified nanosilica particles is narrow, there are few large particles, and they are not easy to settle in the resin medium, which improves the storage stability of the resin dispersion; smaller particle sizes There are also few nanoparticles, and the viscosity of the resin dispersion will not be too high, which is conducive to increasing the solid content of the silica particles; and the number of effective nanoparticles is relatively high.
  • the particle size variation coefficient of the modified nanosilica particles can be ⁇ 12, ⁇ 10%, ⁇ 5%, or even ⁇ 2%.
  • the total content of metal ion impurities in the resin dispersion is less than 10 ppm, the content of single metal ion impurities is less than 3 ppm, and the content of halogen ions is less than 3 ppm.
  • the above-mentioned modified nano-silica particles can be produced by an improved alkoxy silicon hydrolysis method, and there are fewer impurity ions in the resin dispersion. At the same time, the content of impurity ions is much lower than that of SiO 2 sol produced by the water glass method. , this resin dispersion is particularly suitable for use in the field of semiconductor packaging that requires high purity of raw materials.
  • impurity ions in the resin dispersion usually include metal ions such as Na, K, Fe, and Al originating from the reaction vessel and stirring mechanism, and NH 4 + , halogen ions, etc. originating from some reaction raw materials.
  • the SiO 2 particles in the silica sol currently produced from water glass as raw material have a large coefficient of variation in particle size and a high content of impurity ions (especially alkali metal ions and halogen ions).
  • the modified nanometer dioxide provided in this application Silicon particles do not have these problems with SiO 2 particles produced by the water glass method. At the same time, they break through the limitation of low true density of SiO 2 particles produced by the conventional alkoxy silicon hydrolysis method, and do not require organic amines to stabilize SiO 2 particles. , Therefore, the modified nanosilica particles provided by this application can take into account the advantages of the water glass method preparation process and the alkoxy silicon hydrolysis method, that is, taking into account high true density, narrow particle size distribution, and high purity.
  • the modified nanosilica particles in this application may be the result of modification of the surface of the nanosilica particles with an organosilicon compound.
  • the mass of the organic silicon compound is 0.3-15 wt% of the mass of the nano-silica. This helps to improve the compatibility of modified nanosilica particles in the resin medium.
  • the above-mentioned organosilicon compound may include a silane coupling agent.
  • silane coupling agent usually refers to a compound formed by a central silicon atom, a water-decomposable group (such as an alkoxysilyl group) and an organic functional group.
  • Silane coupling agents are generally alkoxysilane, and the structural formula can be expressed as generally Y-Si(R 1 )(R 2 )(R 3 ), at least one of R 1 , R 2 , and R 3 is an alkoxy group, Y Represents an organic functional group, which is reactive or compatible with organic matter.
  • the alkoxy group connected to the Si atom is reactive with inorganic matter. It decomposes into silicon hydroxyl group Si-OH when exposed to water. Si-OH can be combined with Si-OH through dehydration and condensation. -OH on the surface of SiO2 particles form chemical bonds.
  • the organosilicon compound is a silane coupling agent with at least one group selected from the group consisting of alkyl, phenyl, vinyl, (meth)acryloyloxy, epoxy, and amine groups.
  • the above-mentioned Y contains an alkyl group, a phenyl group, a vinyl group, a (meth)acryloyloxy group, an epoxy group, and an amino group.
  • the amine group includes primary amine group (ie, -NH 2 ), secondary amine group, etc.
  • the (meth)acryloyloxy group specifically includes an acryloyloxy group and a methacryloyloxy group.
  • the silane coupling agent can be an alkoxy group having an alkyl group such as trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, etc.
  • Silane Silane; phenyldimethylmethoxysilane, phenyltrimethoxysilane, phenethyltrimethoxysilane and other alkoxysilanes with phenyl group; vinyltrimethoxysilane, vinyltriethoxysilane , vinyltris( ⁇ -methoxyethoxy)silane and other alkoxysilanes with vinyl groups; ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -acryloyloxypropyltrimethoxysilane Alkanes with (meth)acryloyloxy groups such as silane, ⁇ -(methacryloyloxypropyl)methyldimethoxysilane, ⁇ -methacryloyloxypropyltriethoxysilane, etc.
  • the embodiments of the present application also provide a resin dispersion, which contains modified nano-silica particles, a dispersion resin and a co-dispersing agent, wherein the modified nano-silica particles are surface-modified with an organosilicon compound.
  • Nano-silica the true density of the modified nano-silica particles is 2.0-2.2g/ cm3 ; the total content of metal ion impurities in the resin dispersion is less than 10 ppm, the content of single metal ion impurities is less than 3 ppm, halogen The content of ions is less than 3ppm.
  • the silica sol currently produced using water glass as raw material has a high content of impurity ions (especially alkali metal ions and halogen ions).
  • impurity ions especially alkali metal ions and halogen ions.
  • the dispersion medium of the silica sol is replaced by water and/or organic solvents with dispersion resin, the resulting resin dispersion will The impurity content is also high; the true density of silica sol produced by the sol-gel method using silicon alkoxide as raw material is usually low and difficult to exceed 1.8g/cm 3 .
  • the true density of the modified nano-silica particles contained in the resin dispersion provided by this application can be as high as 2.0-2.2g/cm 3 , breaking through the true density of SiO 2 particles produced by the conventional alkoxy silicon hydrolysis method.
  • the resin dispersion can take into account the advantages of high true particle density and low impurity content.
  • the resin dispersion does not contain organic amines.
  • this application does not require organic amines to stabilize the resin dispersion.
  • the true density of the modified nanosilica particles can also be ensured to be high, and the particle size distribution is also narrow.
  • organic amine-free resin dispersion is mixed with epoxy resin, it will not affect the storage stability of the mixed material and the quality reliability of the cured product.
  • the modified nanosilica particles of the present application can also have characteristics such as narrow particle size distribution, good dispersibility in resin dispersion, and high solid content.
  • the particle size variation coefficient of the modified nanosilica particles known based on transmission electron microscope photos is less than or equal to 15%. This may reflect the narrow size distribution of the particles.
  • the ratio of the average particle size of the modified nanosilica particles in the resin dispersion to its average primary particle size measured based on the dynamic light scattering method is less than or equal to 2.0. This reflects that the particles are well dispersed in the resin dispersion.
  • the mass percentage of modified nano-silica particles in the resin dispersion is 39-60wt%. It can reflect that the content of particles in the resin dispersion is relatively high. The beneficial effects brought by these features can be found in the previous description of this application.
  • the embodiments of the present application also provide a modified silica sol, including modified nano-silica particles, wherein the modified nano-silica particles are nano-silica surface-modified with an organosilicon compound, and the modified nano-silica particles
  • the true density of nanometer silica particles is 2.0-2.2g/cm 3 ; the total content of metal ion impurities in the modified silica sol is less than 10ppm, the content of single metal ion impurities is less than 3ppm, and the content of halogen ions is less than 3ppm.
  • the silica sol produced using water glass as raw material has a high content of impurity ions (especially alkali metal ions and halogen ions); the true density of silica sol produced using alkoxy silicon as raw material using the sol-gel method is usually lower than Low, difficult to exceed 1.8g/cm 3 .
  • the true density of the modified nano-silica particles contained in the modified silica sol provided by this application can be as high as 2.0-2.2g/cm 3 , breaking through the limitations of SiO 2 particles produced by conventional alkoxy silicon hydrolysis methods. Due to the limitation of true density, there is no need to calcine the particles to achieve densification.
  • the modified nano-silica particles When the modified nano-silica particles are subsequently mixed with resin materials, they can withstand high-speed shearing forces without being damaged, which is particularly suitable for For application scenarios requiring high mechanical properties. At the same time, the impurity content in the modified silica sol is low, and there is no problem of high impurity content caused by the water glass preparation method. When the modified silica sol is used in packaging materials after certain treatment, it is introduced The impurity content in the packaging material is also less, which can greatly reduce corrosion of electronic components and metal circuits and improve packaging reliability. Therefore, the modified silica sol can take into account the advantages of high particle true density and low impurity content.
  • the above-mentioned modified silica sol can be produced by an improved alkoxy silicon hydrolysis method.
  • silicon alkoxide as the silicon source, in a reaction medium with a mass ratio of alcohol to dilute ammonia water of 8:1-40:1, a silica sol with high true density and low impurity content can be produced.
  • the modified silica sol does not contain organic amines.
  • Organic amines are usually introduced during the production of SiO 2 particles using alkoxy silicon hydrolysis to improve their true density and SiO 2 sol stability.
  • no organic amines were used when preparing SiO 2 particles, and there is no need to add organic amines to the obtained silica sol to stabilize the sol. Therefore, the above-mentioned silica sol does not contain organic amines, and at the same time, the modified nanometer dioxide The true density of silicon particles can be higher and the particle size distribution is narrower.
  • the modified silica sol that does not contain organic amines is mixed with an epoxy resin that is not resistant to alkali, it will not affect the storage stability of the mixture and the quality reliability of the cured product.
  • the particle size variation coefficient of the modified nanosilica particles obtained based on transmission electron micrographs is less than or equal to 15%. This reflects that the particle size distribution of modified nanosilica particles is narrow.
  • the dispersion medium in the modified silica sol is an organic solvent.
  • the organic solvent preferably does not contain alcohol substances, so that when the modified silica sol is mixed with the encapsulating resin material, it can avoid the volatilization of low-boiling point alcohol substances during the curing process of the mixed materials.
  • the cured product produces pores, which affects the density of the package.
  • the dispersion medium in the modified silica sol includes organic solvents and dispersion resins.
  • the ratio of the average dispersed particle size of the modified nanosilica particles in the dispersion medium and its average primary particle size measured based on the dynamic light scattering method may be less than or equal to 2.0.
  • the ratio of the average dispersed particle size of conventional SiO 2 particles in the organic solvent to its average primary particle size is easily made smaller (for example, ⁇ 2), but the dispersion medium is replaced by an organic solvent + dispersion
  • the compatibility of conventional SiO 2 particles in the dispersion medium is not very good, the average dispersed particle size in it is large, and the above ratio is difficult to be less than 3; and this application provides
  • the modified nanosilica particles have better dispersion in resin-containing dispersion media, and the above ratio can be ⁇ 2, or even ⁇ 1.6.
  • the average particle size of the modified nanosilica particles in the two dispersion media shown above can reach 15nm-150nm, for example, it can specifically reach 15nm-100nm, 18nm- 80nm, 18-50nm, etc.
  • the embodiments of this application also provide a preparation method for the above-mentioned modified silica sol, which includes the following steps:
  • alcohol, dilute ammonia water and silicon alkoxide are stirred and reacted at a temperature above 40°C, so that the silicon alkoxide can be hydrolyzed and condensed to obtain a sol containing SiO 2 particles.
  • controlling the mass ratio of alcohol to dilute ammonia water in the range of 8:1-40:1 can ensure that the silicon alkoxide can be fully hydrolyzed, and rely on the solvation effect of alcohol and the catalytic effect of an appropriate amount of dilute ammonia water.
  • the hydrolysis rate of silicon alkoxide can be controlled to control the nucleation rate of SiO 2 appropriately.
  • the growth rate of SiO 2 can be controlled, so that the TEM particle size variation coefficient can be small and the density can be high ( Nanoscale SiO 2 particles with true density in the range of 2.0-2.2g/ cm3 ).
  • this application uses silicon alkoxide as the raw material for preparing silica sol. This raw material will hardly introduce impurities such as alkali metal ions and halogen ions, and the purity of the silica sol prepared by it is also relatively high; add The above-mentioned parameter control of the mass ratio of alcohol to dilute ammonia water and stirring speed can also ensure that impurities originating from redundant raw materials and experimental equipment are not easily introduced during the nucleation and growth process of SiO 2 particles at an appropriate speed.
  • alkali metal silicates, chlorine-containing silanes and other materials containing alkali metal and chlorine impurities are not used.
  • the speed of the stirring reaction is controlled within a certain range, and high true density and low impurity content can be synthesized. , low particle size variation coefficient and good dispersion silica sol.
  • the mass ratio of alcohol to dilute ammonia water can be specifically 10:1, 12:1, 15:1, 20:1, 25:1, 30:1 or 35:1.
  • the mass ratio of alcohol to dilute ammonia is 20:1-40:1, which can ensure a more appropriate nucleation speed of SiO 2 and thereby obtain nanometer particles with a smaller coefficient of variation in TEM particle size and a higher true density. grade SiO 2 particles.
  • dilute ammonia water is used as a catalyst to promote the hydrolysis of alkoxysilane instead of organic amine as a catalyst, and the mass ratio of dilute ammonia water and alcohol is controlled within the above range. It is easier to control the particle size of SiO 2 particles at the nanometer level. And ammonia is easier to remove from SiO2 , ensuring its high purity. It can be understood that the silica sol obtained in this application does not contain organic amines.
  • the concentration of ammonia in the reaction mixture is less than or equal to 0.5mmol/g (ammonia specifically refers to the solute in dilute ammonia water, and the concentration refers to the molar amount of ammonia relative to alcohol, dilute ammonia water, alkoxy group Proportion of the total added mass of silicon).
  • ammonia specifically refers to the solute in dilute ammonia water
  • concentration refers to the molar amount of ammonia relative to alcohol, dilute ammonia water, alkoxy group Proportion of the total added mass of silicon.
  • the rate of ammonia-catalyzed hydrolysis of the silicon source can be reduced, which in turn is conducive to slowing down the growth rate of SiO 2 particles and growing SiO 2 particles with high density and relatively concentrated particle size distribution.
  • the original concentration of the dilute ammonia solution used may be less than or equal to 10wt%.
  • the above stirring speed may specifically be 250, 300, 400, 500, 600, 700, 720 or 750 rpm, etc.
  • the temperature of the above-mentioned stirring reaction should be above 40°C and lower than the boiling point of the mixed reaction solution, so as to ensure that the active silicic acid hydrolyzed into silicon alkoxide can polymerize smoothly and obtain SiO 2 particles with a certain density.
  • the alcohol may be a monoalkyl alcohol or a dihydric alkyl alcohol having 1 to 10 carbon atoms.
  • the alcohol may include at least one of methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, pentanol, ethylene glycol, propylene glycol, butylene glycol, and the like.
  • silicon alkoxide refers to a substance having an alkoxy group as a substituent of a silicon atom.
  • the number of carbon atoms of the alkoxy group may be 1-4.
  • the Si atom may have 4 alkoxy substituents, or 1-3 alkoxy substituents.
  • the silicon alkoxide may also have 1-3 other substituents, such as an alkyl group with 1-6 carbon atoms, or an aryl group, etc.
  • silicon alkoxides may include tetramethoxysilane (TMOS, also known as methyl orthosilicate), tetraethoxysilane (TEOS, also known as ethyl orthosilicate), methyltrimethoxysilane Silane (also known as “methyltrimethyl silicate”), methyltriethoxysilane (also known as “methyltriethyl silicate”), dimethyldimethoxysilane (also known as "silicic acid”) One or more of "dimethyl dimethyl ester”), diethoxydimethylsilane (DMDS, also known as "dimethyl diethyl silicate”), etc.
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • methyltrimethoxysilane Silane also known as "methyltrimethyl silicate”
  • methyltriethoxysilane also known as “methyltriethyl silicate”
  • the silicon alkoxide is mixed with the alcohol and dilute ammonia water at an addition rate of 1.0-40.0g/(min ⁇ L container). Adding the silicon source at this rate will help ensure that the silicon source has a suitable hydrolysis speed and diffusion speed, ensure that the particle size of the grown SiO 2 particles will not be too large, reduce particle aggregation, and ensure that the silicon source can fully react and improve The yield of SiO 2 particles is improved without leaving unhydrolyzed alkoxy groups inside the SiO 2 particles to reduce their density.
  • step (2) adding a silicone modifier can form a modification layer on the nanosilica particles to improve their stability in the sol.
  • the mass of the added silicone modifier can be 0.3-15wt% of the mass of the nano-silica particles, which can ensure the good stability of the modified nano-silica particles contained in the obtained modified silica sol. This will help improve the compatibility of the particles in the resin medium and increase the solid content of the particles in the resin medium.
  • impurities in the system may include metal ion impurities such as Na, K, Fe, and Al originating from reaction raw materials, solvents and auxiliaries, reaction vessels, and stirring mechanisms, as well as NH 4 + and NH 4 + originating from some reaction raw materials.
  • metal ion impurities such as Na, K, Fe, and Al originating from reaction raw materials, solvents and auxiliaries, reaction vessels, and stirring mechanisms, as well as NH 4 + and NH 4 + originating from some reaction raw materials.
  • Halogen ions there may also be unreacted modifiers and silicon sources.
  • Halogen ions are generally derived from silicon alkoxides, which are generally obtained through a series of reactions of SiCl 4 . Among them, impurities can be removed by ion exchange.
  • the method for removing ammonia water in the system may include distillation, ion exchange, etc., and it is preferable to heat it. Ammonia volatilizes.
  • the ammonia when it is necessary to replace the medium (water and alcohol) in the modified silica sol obtained in the above step (2) with other non-alcoholic organic solvents, the ammonia can be replaced while replacing the alcohol. Distilled away with water. At this time, what is obtained is a modified silica sol using a non-alcoholic organic solvent as the dispersion medium.
  • step (2) recovering the alcohol in the system under reduced pressure, removing ammonia and water in the system, and adding non-alcoholic organic solvents thereto to replace the residual alcohol in the system. alcohol and water to obtain a modified silica sol dispersed in non-alcoholic organic solvents.
  • a dispersion resin can also be added to the modified silica sol dispersed in non-alcoholic organic solvents to obtain modified nanosilica using dispersion resin + non-alcoholic organic solvent as a dispersion medium. sol.
  • the modified nano-silica sol at this time is equivalent to the resin dispersion of modified nano-silica particles mentioned above in this application (when the co-dispersing agent is an organic solvent).
  • the embodiments of the present application also provide a preparation method for the above-mentioned resin dispersion, including the following steps:
  • alcohol, dilute ammonia water and silicon alkoxide are mixed, and the mass ratio of alcohol to dilute ammonia water is controlled in the range of 8:1-40:1, which can ensure that the silicon alkoxide can be fully hydrolyzed, and with the help of
  • the combined effect of the solvation effect of alcohol and the catalytic effect of an appropriate amount of dilute ammonia water can control the hydrolysis of silicon alkoxide to form SiO 2 nuclei at the appropriate nucleation speed; stirring at an appropriate speed at a temperature above 40°C can control the alkane.
  • Oxygen-based silicon is uniformly diffused in the reaction medium and polymerized and deposited at a suitable rate around the formed core to have a suitable SiO 2 growth rate.
  • this application uses silicon alkoxide as the raw material for preparing silica sol.
  • This raw material hardly introduces inorganic impurity ions such as alkali metal ions and halogen ions, and the purity of the silica sol prepared by it is also relatively high. ; Coupled with the above-mentioned parameter control of the mass ratio of alcohol to dilute ammonia water and stirring speed, it can also ensure that impurities originating from redundant raw materials and experimental equipment are not easily introduced during the nucleation and growth process of SiO 2 particles at an appropriate speed.
  • step (3) the recovery of alcohol can be achieved by distillation under reduced pressure. While recovering the alcohol, all or most of the ammonia can be distilled off along with the alcohol. Even if a small amount of ammonia is not removed during alcohol recovery, the residual ammonia can be removed when a co-dispersing agent is subsequently added to replace the alcohol.
  • the added dispersant includes one or more of the aforementioned ether substances, ketone substances, ester substances, amide substances, and nitrile substances.
  • the mass ratio of the dispersant dispersion liquid of the modified nanosilica particles to the dispersion resin can be 5:6-2:1. At this time, it helps to ensure that the obtained resin dispersion contains more modified nano-silica particles, an appropriate amount of co-dispersing agent and less dispersing resin, thereby improving the dispersion of modified nano-silica particles in the resin. dispersion in the liquid and increase its mass proportion.
  • the mass percentage of the modified nanosilica particles in the resin dispersion may be 39-60 wt%, for example, 48-60 wt%.
  • the mass percentage of the dispersant in the above-mentioned resin dispersion is 0.3-10wt%.
  • the mass percentage of the dispersion resin in the above-mentioned resin dispersion is 30-60wt%.
  • the dispersion resin used includes at least one of epoxy resin, phenolic resin, acrylic resin, polysiloxane, polyamic acid, and polyurethane monomers or prepolymers.
  • the dispersion resin is preferably the same type of material as the body resin material.
  • the main resin material is epoxy resin
  • the dispersed resin in the resin dispersion is preferably a monomer of epoxy resin.
  • the embodiments of the present application also provide a resin composition, including a host resin material and the resin dispersion of the modified nanosilica particles mentioned above in the embodiments of the present application.
  • the modified nano-silica particles can be evenly dispersed in the liquid resin composition.
  • the viscosity and fluidity of the resin composition are appropriate, and can be smoothly coated and cured to form a coating with good morphology and strong applicability. , at the same time, the resin composition has good transparency and can be used in the preparation of coatings that require high light transmittance.
  • the filling rate of the particles in the resin composition is correspondingly high, which ensures that the cured product of the resin composition has low thermal expansion. coefficient; in addition, less dispersed resin is brought into the resin composition, which is more conducive to the formulation design of the resin composition.
  • the above-mentioned resin composition is particularly suitable for forming the underfill layer 202 and the plastic package 30 of the above-mentioned semiconductor package.
  • the underfill glue layer 202 can be formed by dispensing and filling the above-mentioned liquid resin composition and then solidifying it. For example, curing can occur by exposure to heat or exposure to ultraviolet light.
  • the plastic encapsulated body 30 can be converted into a semi-cured molding compound that is easy to store (the main resin is not completely cross-linked and solidified at this time) by first kneading, aging and other treatments.
  • the molding compound can be in the form of a sheet or Groups etc.
  • the molding compound can be processed into a cured product with a certain structure and appearance through common molding processes such as transfer molding, compression molding or injection molding, and the main resin is completely cross-linked and solidified during the molding process.
  • the main resin material includes epoxy resin
  • the resin composition also includes a curing agent.
  • Epoxy resin is a resin material commonly used in the field of semiconductor packaging. When heated, the epoxy resin and the curing agent in the resin composition can react chemically and solidify to form a cured product with a certain shape.
  • Curing agents suitable for epoxy resins may include one or more of anhydride curing agents, amine curing agents, phenolic resins, etc.
  • the epoxy resin as the main resin is a prepolymer.
  • the dispersion resin contained in the above-mentioned resin dispersion liquid may be a monomer or prepolymer of epoxy resin, and the molecular weight of the epoxy resin as the main resin is generally greater than the molecular weight of the epoxy resin prepolymer as the dispersion resin. To ensure good thermodynamic properties of the resin composition.
  • the above-mentioned resin composition also includes fillers of different particle sizes, such as submicron or micron-sized silica, alumina, aluminum nitride, silicon nitride, boron nitride, etc.
  • fillers of different particle sizes such as submicron or micron-sized silica, alumina, aluminum nitride, silicon nitride, boron nitride, etc.
  • the above-mentioned resin composition also includes one or more of coupling agents, flow improvers, thickeners, flame retardants, colorants, ion trapping agents, stress absorbers, release agents, etc. Additives. These additives can be added as appropriate.
  • the embodiments of the present application also provide a cured product, which is obtained by curing the resin composition described above in the embodiments of the present application.
  • An embodiment of the present application also provides a semiconductor package, including the cured product described above in the embodiment of the present application.
  • a schematic structural diagram of the semiconductor package is shown in FIG. 1 , and the specific structure can be found in the previous description of this application.
  • the underfill layer 202 and the plastic package 30 in the semiconductor package 100 may be a cured product of the resin composition.
  • the above-mentioned resin composition and its cured product are not limited to use in semiconductor packages, but can also be used in other polymer materials that require the use of nano-silica particles, such as adjacent components in other devices.
  • a resin dispersion of modified nanosilica particles which contains the following mass percentages of each component: 60wt% modified nanosilica particles, 30wt% bisphenol F with an average degree of polymerization n less than 0.5 Type epoxy resin, 10wt% dioxane as dispersant.
  • the modified nano-silica particles are nano-silica surface-modified with 2wt% of 3-glycidoxypropyltrimethoxysilane.
  • the modified nano-silica was measured based on the dynamic light scattering method.
  • the average dispersed particle size D2 of the particles in the resin dispersion is 18nm.
  • the specific surface area S of the dried modified nanosilica particles measured is 172.27m 2 /g.
  • the average primary particle size D1 in the liquid is 15.79nm, so D2/D1 is 1.14; the particle size variation coefficient of the modified nanosilica particles based on TEM is 10%; the dry modified nanosilica particles The true density is 2.0g/cm 3 ; the sodium ion content in the above resin dispersion is 0.329ppm, and the chloride ion content is 0.382ppm.
  • the resin dispersion of modified nanosilica particles provided in Example 1 of the present application has many advantages, such as low impurity content of the resin dispersion, high content of modified nanosilica particles, and Good dispersion, modified nano-silica particles have high true density and uniform particle size distribution.
  • the preparation method of the above-mentioned resin dispersion liquid includes the following steps:
  • Figure 2 is a TEM photograph of the resin dispersion of modified nanosilica particles provided in Example 1 of the present application. It can be seen that the modified nanosilica particles have good dispersion in acrylic resin and there is no particle agglomeration. Based on this photo, it can be calculated that the dispersion coefficient of the TEM particle size of the particle is 10%.
  • Figure 3 is a particle size distribution diagram of the resin dispersion of Example 1 of the present application measured based on the dynamic light scattering method. It can be understood from Figure 3 that the modified nano-silica particles in the resin dispersion were measured using the dynamic light scattering method. The average dispersed particle size (ie, particle size D50) is 18 nm.
  • resin dispersion Mix 10g of the above resin dispersion with 18g of bisphenol F epoxy resin, 11g of amine curing agent, 60g of silica filler with an average particle size of 0.5 ⁇ m, and 1g of silane coupling agent to obtain a ring Oxy resin composition, the epoxy resin composition is heated to 160° C. and cured to obtain a cured product of the epoxy resin composition. In addition, the epoxy resin composition is used to underfill the semiconductor chip disposed on the substrate by dispensing, and then heated to 160° C. for solidification to form an underfill glue layer, which is the cured product of the above-mentioned epoxy resin composition. .
  • the cured product of the above epoxy resin composition was sliced and analyzed. From the slice scanning electron microscope photo ( Figure 4), it can be seen that the silica particles are evenly dispersed in the cured product, and the micron-sized silica particles are closely packed together. There are nano-sized silica particles.
  • a resin dispersion of modified nanosilica particles which contains the following mass percentages of each component: 39.7wt% modified nanosilica particles, 60wt% bisphenol with an average degree of polymerization n less than 0.5 Type A epoxy resin, 0.3wt% ethylene glycol methyl ether as dispersant.
  • the modified nano-silica particles are nano-silica surface-modified with 5wt% phenyltriethoxysilane modifier. Based on the dynamic light scattering method, the modified nano-silica particles were measured in the The average dispersed particle size D2 in the resin dispersion is 48nm.
  • the specific surface area S of the dried modified nanosilica particles measured based on the nitrogen adsorption method is 90.67m 2 /g.
  • the average primary particle size D1 is 30nm, so D2/D1 is 1.60; the particle size variation coefficient of the modified nanosilica particles based on TEM is 11%; the true density of the dried modified nanosilica particles is 2.1 g/cm 3 ; the sodium ion content in the above resin dispersion is 1.357ppm, and the chloride ion content is 0.260ppm.
  • the resin dispersion of modified nanosilica particles provided in Example 2 of the present application has many advantages, such as low impurity content of the resin dispersion, high content of modified nanosilica particles, and Good dispersion, modified nano-silica particles have high true density and uniform particle size distribution.
  • the preparation method of the above-mentioned resin dispersion liquid includes the following steps:
  • modified silica sol with a chloride ion content of 0.260ppm.
  • the TEM particle size dispersion coefficient, true density, average dispersed particle size, etc. of the modified silica particles contained in the modified silica sol are basically the same as step 1).
  • Figure 5 is a TEM photograph of the resin dispersion of modified nano-silica particles provided in Example 2 of the present application. It can be seen that the modified nano-silica particles have good dispersion in bisphenol A-type epoxy resin. There is no particle agglomeration. According to this photo, the dispersion coefficient of the TEM particle size of the particles can be calculated to be 11%.
  • Figure 6 is a particle size distribution diagram of the resin dispersion of Example 2 of the present application measured based on the dynamic light scattering method. It can be understood from Figure 5 that the modified nano-silica particles in the resin dispersion were measured using the dynamic light scattering method. The average dispersed particle size (ie, particle size D50) is 48 nm.
  • a resin dispersion of modified nanosilica particles which contains the following mass percentages of each component: 50wt% modified nanosilica particles, 45wt% phenolic resin prepolymer, 5wt% acetonitrile Dispersant aid.
  • the modified nano-silica particles are nano-silica surface-modified with 10wt% phenyltriethoxysilane modifier. Based on the dynamic light scattering method, the modified nano-silica particles were measured in the The average dispersed particle size D2 in the resin dispersion is 80nm.
  • the specific surface area S of the dried modified nanosilica particles measured based on the nitrogen adsorption method is 44.2m 2 /g.
  • the average primary particle size D1 in the resin dispersion is 61.5nm, so D2/D1 is 1.3; the particle size variation coefficient of the modified nanosilica particles based on TEM is 3%; dry modified nanosilica The true density of the particles is 2.15g/cm 3 ; the sodium ion content in the above-mentioned resin dispersion is 0.87ppm, and the chloride ion content is 0.31ppm.
  • the resin dispersion of modified nanosilica particles provided in Example 3 of the present application has many advantages, such as low impurity content of the resin dispersion, high content of modified nanosilica particles, and Good dispersion, modified nano-silica particles have high true density and uniform particle size distribution.
  • the preparation method of the above-mentioned resin dispersion liquid includes the following steps:

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Abstract

Des modes de réalisation de la présente invention concernent une dispersion de résine de particules de nano-silice modifiées et un procédé de préparation et une application de la dispersion de résine. La dispersion de résine contient des particules de nano-silice modifiées ayant un rapport massique de 39 à 60 % en poids, une résine de dispersion et un agent d'aide à la dispersion ; la surface des particules de nano-silice modifiées est modifiée avec un composé d'organosilicium ; et le rapport de la taille de particule moyenne des particules de nano-silice modifiées mesurées au moyen d'un procédé de diffusion de lumière dynamique à la taille de particule primaire moyenne de celles-ci est inférieur ou égal à 2,0. Les particules de nano-silice modifiées présentent une bonne monodispersité et un rapport massique élevé dans la dispersion de résine, et lorsque la dispersion de résine est utilisée dans un matériau de résine d'emballage, les particules de nano-silice modifiées peuvent être uniformément dispersées dans le matériau, afin que la fluidité du matériau d'emballage ne serait pas significativement réduite, et le coefficient de dilatation thermique du matériau d'emballage peut être efficacement réduit. Les modes de réalisation de la présente invention concernent en outre un sol de silice modifié et son procédé de préparation.
PCT/CN2023/090707 2022-04-29 2023-04-25 Dispersion de résine de particules de nano-silice modifiées et procédé de préparation et application de dispersion de résine Ceased WO2023208006A1 (fr)

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JP2013126925A (ja) * 2011-12-16 2013-06-27 Jgc Catalysts & Chemicals Ltd シリカ粒子、その製造方法および半導体実装用ペースト
JP2014209621A (ja) * 2013-03-29 2014-11-06 株式会社アドマテックス ３次元実装型半導体装置、樹脂組成物及びその製造方法
KR20150050953A (ko) * 2013-11-01 2015-05-11 한국전기연구원 졸겔 기법을 이용한 에폭시-실리카 나노입자 하이브리드 수지 및 이의 제조방법과, 이를 이용한 고분산 에폭시-무기 나노/마이크로 입자 하이브리드 수지 및 이의 제조방법

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