Slurry and preparation method and application thereof

Abstract

The embodiment of the invention provides slurry as well as a preparation method and application thereof. The slurry comprises inorganic particles and a liquid dispersion medium, in the slurry, the D50 particle size of the inorganic particles is in the range of 0.25-1.5 [mu] m, the ratio of the D50 particle size to the D90 particle size of the inorganic particles is greater than 0.5, and the ratio of the mode diameter to the D90 particle size of the inorganic particles is greater than 0.55. Therefore, when the D50 particle size of the inorganic particles in the slurry is fixed, the D90 is as small as possible, and the particle size distribution is concentrated near the smaller D90, so that the slurry has the characteristics of low settleability, high solid content and low viscosity, and the reliability of the slurry in the packaging field is improved.

Description

Technical Field

[0001] The present application relates to the technical field of electronic device preparation, and in particular to a slurry, a preparation method thereof, and an application thereof. Background Art

[0002] As electronic devices develop towards miniaturization and higher functionality, the components they carry are required to be smaller and more integrated. Consequently, the requirements for various packaging materials used to package these components (such as chip attach adhesives and packaging substrates) are becoming increasingly stringent, requiring them to have a low coefficient of thermal expansion to improve packaging reliability. Inorganic particles such as SiO2 can be added to the resin component of the packaging material to reduce the thermal expansion coefficient of the packaging material.

[0003] Inorganic particles with an average particle size of less than 2 μm are more suitable for the packaging of miniaturized electronic components, but their small particle size and high surface energy make their powders easily agglomerated and difficult to disperse well in the resin material. Adding them to the resin material in the form of a slurry with a liquid dispersion medium can help reduce their agglomeration before use. However, the prepared inorganic particle slurry is prone to sedimentation during storage, especially when the powder particle size distribution is improperly controlled or the slurry concentration is not high. After sedimentation, it is generally difficult to redisperse. Generally, low-concentration slurries are easy to disperse, but the sedimentation rate of inorganic particles is fast, especially when the content of particles with relatively large particle size is high; small-sized inorganic particles can increase the viscosity of the slurry and slow down the sedimentation caused by large-sized particles, but excessive content of small-sized inorganic particles will make the slurry too viscous, making it impossible to obtain a slurry with a high solid content, resulting in little effect on improving the reliability of the packaging material and increasing the difficulty of removing the subsequent liquid dispersion medium. Therefore, it is necessary to provide an inorganic particle slurry that can take into account the characteristics of high solid content and non-settling. Summary of the Invention

[0004] In view of this, the embodiments of the present application provide an inorganic particle slurry that can take into account the characteristics of high solid content, low sedimentation, and low viscosity, so as to improve its packaging reliability in the packaging field.

[0005] A first aspect of an embodiment of the present application provides a slurry comprising inorganic particles and a liquid dispersion medium, wherein in the slurry, the D50 particle size of the inorganic particles is in the range of 0.25 μm-1.5 μm, the ratio of the D50 particle size to the D90 particle size of the inorganic particles is greater than 0.5, and the ratio of the mode diameter to the D90 particle size of the inorganic particles is greater than 0.55.

[0006] When the slurry provided in the present application meets the above conditions, it can ensure that when the D50 particle size of the inorganic particles in the slurry is constant, its D90 is as small as possible, and the particle size at the highest frequency is close to the smaller D90, so that the slurry contains more inorganic particles with good dispersion while still having low viscosity and high fluidity, that is, taking into account low sedimentation, high solid content and low viscosity.

[0007] In some embodiments of the present application, the ratio of the D50 particle size to the D90 particle size of the inorganic particles is in the range of 0.51-0.80. A larger ratio of D50 to D90 than 0.5 indicates a closer relationship between D90 and D50, which helps to ensure fewer large particles in the slurry.

[0008] In some embodiments of the present application, the ratio of the mode diameter to the D90 particle diameter of the inorganic particles is in the range of 0.56-0.85. In this case, the closer the mode diameter is to the D90 particle diameter, the more effective it is in reducing the slurry viscosity and increasing the solid content.

[0009] In the embodiment of the present application, the mode diameter of the inorganic particles is within the range of 0.3 μm to 1.65 μm. This ensures that the most abundant particles in the slurry have an appropriate particle size and are mixed with particles of other particle sizes, thereby ensuring that there are not too many small particles in the slurry and that the large particle size does not deviate too much from the mode diameter, which helps the slurry achieve low viscosity, high solids content, and low sedimentation properties.

[0010] In the embodiment of the present application, the D90 particle size of the inorganic particles is in the range of 0.5 μm-2.5 μm. When the above particle size requirements are met, controlling the D90 particle size of the inorganic particles in an appropriate range can further ensure that there are not too many large inorganic particles in the slurry.

[0011] In the embodiment of the present application, the inorganic particles are m 2 The product of the specific surface area in μm and the D50 particle size of the inorganic particles in μm is within the range of 2.6-4.5. This helps to ensure that there are an appropriate number of small particles in the slurry, avoiding both excessive ultrafine particles that increase the slurry viscosity and excessive large particles that make the slurry prone to sedimentation.

[0012] In the embodiment of the present application, the specific surface area of ​​the inorganic particles is 3.1m 2 / g-8.0m 2 This ensures that the inorganic particles have a suitable particle size distribution, which helps the slurry to have a low viscosity even when it contains a relatively high content of inorganic particles.

[0013] In an embodiment of the present application, the mass percentage of the inorganic particles in the slurry is greater than or equal to 60 wt %. When the slurry meets the above-mentioned particle size characteristics, the inorganic particles have good dispersibility therein, and the mass percentage of the inorganic particles in the slurry can be relatively high. In some embodiments of the present application, the mass percentage of the inorganic particles in the slurry is 70-90 wt %.

[0014] In some embodiments of the present application, the surface of the inorganic particles is modified with a surface modifier, wherein the surface modifier includes one or more of a silane coupling agent and a silazane. Modification with the surface modifier can improve the compatibility between the inorganic particles and the liquid dispersion medium, further reduce the probability of particle sedimentation, and increase the solid content of the slurry.

[0015] In the embodiment of the present application, the mass ratio of the surface modifier to the inorganic particles is: 2 When preparing surface-modified inorganic particles, this parameter range helps guide the preparation of a surface modifier with an appropriate amount of surface modification, thereby effectively improving the dispersion stability of the particles while not introducing too much surface modifier and reducing the particle content in the slurry.

[0016] A second aspect of the embodiments of the present application provides a resin composition, which includes a resin material and the slurry as described in the first aspect of the embodiments of the present application.

[0017] In an embodiment of the present application, the resin material includes epoxy resin, and the resin composition further includes a curing agent.

[0018] The third aspect of the embodiments of the present application provides the use of the slurry described in the first aspect of the embodiment of the present application and the resin composition described in the second aspect of the embodiment of the present application in the sealed packaging of electronic components.

[0019] Specifically, the application in the sealed packaging of electronic components includes at least one of making a core board for a packaging substrate, a build-up film for a packaging substrate, a solder mask ink layer on a packaging substrate, and an adhesive layer for fixing electronic components, but is not limited thereto.

[0020] A fourth aspect of the present application provides a packaging material for sealing electronic components. The packaging material comprises the resin composition described in the second aspect of the present application and / or a cured product of the resin composition. Using the resin composition provided in the present application as a packaging material for electronic component packaging can enhance the packaging effect and improve the service reliability of the electronic components.

[0021] A fifth aspect of the present invention provides a sealed package comprising a cured product of the resin composition described in the second aspect of the present invention. The sealed package of the present invention is encapsulated using the cured product of the resin composition provided in the present invention and has high service reliability. The resin composition can be cured to form a cured product of various shapes as needed.

[0022] In an embodiment of the present application, the sealed package includes a packaging substrate and electronic components disposed on the packaging substrate. The packaging substrate includes a core substrate and a build-up film and a solder mask ink layer sequentially stacked on opposite sides of the core substrate. At least one of the core substrate, the build-up film, and the solder mask ink layer includes the cured product. The electronic components include, but are not limited to, chips. When the electronic components are chips, the sealed package is a chip packaging structure.

[0023] In some embodiments of the present application, the electronic component is a chip, at least one chip is provided on the packaging substrate, and the chip bonding film provided between the chip and the packaging substrate and / or between adjacent chips includes the cured product.

[0024] A sixth aspect of the present application further provides an electronic device comprising a circuit board and the sealed packaging member of the fifth aspect of the present application disposed on the circuit board. The electronic device of the present embodiment employs the sealed packaging member provided in the present embodiment, thereby improving the service reliability of the electronic device.

[0025] The present invention also provides a method for preparing a slurry, comprising:

[0026] Selecting inorganic particle powders with different median particle sizes and a single distribution, mixing the multiple inorganic particle powders, and adding a liquid dispersion medium so that the D50 particle size of the inorganic particles in the resulting slurry is within the range of 0.25 μm to 1.5 μm, the ratio of the D50 particle size to the D90 particle size of the inorganic particles is greater than 0.5, and the ratio of the mode diameter to the D90 particle size of the inorganic particles is greater than 0.55;

[0027] Alternatively, the particle size distribution of the initial slurry containing inorganic particles and a liquid dispersion medium is regulated so that the D50 particle size of the inorganic particles in the slurry obtained after regulation is in the range of 0.25 μm to 1.5 μm, the ratio of the D50 particle size to the D90 particle size of the inorganic particles is greater than 0.5, and the ratio of the mode diameter to the D90 particle size of the inorganic particles is greater than 0.55.

[0028] The preparation method of the slurry is simple and easy to operate, and the slurry with the above-mentioned excellent performance can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 A schematic structural diagram of a sealed package 100 provided in an embodiment of the present application.

[0030] Figure 2 for Figure 1 FIG. 1 is a schematic diagram of a sealed package 100 being arranged on a circuit board.

[0031] Figure 3 A schematic diagram of the structure of the terminal device 200 provided in an embodiment of the present application.

[0032] Figure 4 This is the particle size distribution diagram of the composite particles used to prepare the slurry in Example 1.

[0033] Figure 5 The figure shows the particle size distribution of the powder used to prepare the slurry in Example 2 before and after particle size distribution adjustment. DETAILED DESCRIPTION

[0034] The technical solution of this application will be described below in conjunction with the drawings in the embodiments of this application.

[0035] The slurry formed by dispersing inorganic particles in a liquid dispersion medium is added to a resin material to form a resin composition. Its cured product has a low thermal expansion coefficient and is not easy to warp compared to the cured product of a simple resin material, and the slurry form of the inorganic particles is relatively difficult to agglomerate compared to the powder form. In order to improve the reliability of the cured product of the resin composition, it is generally desired that the solid content of the inorganic particle slurry is higher as much as possible, and the difficulty of removing the liquid dispersion medium derived from the slurry in the subsequent resin composition is reduced. However, when the solid content of the slurry is too high, it is difficult to ensure that the inorganic particles added are fully dispersed, and the sedimentation and agglomeration of the particles will be aggravated instead, and it is impossible to obtain a slurry with good dispersibility and a high real solid content. Therefore, the existing inorganic particle slurry still has problems such as easy sedimentation and low solid content. For this reason, the present application embodiment provides an inorganic particle slurry that can take into account high solid content, not easy sedimentation, and low viscosity characteristics. The resin composition made of the inorganic particle slurry and the resin material can have both appropriate low viscosity and high fluidity, good dispersibility, and can have a lower thermal expansion coefficient CTE after solidification. The resin composition can be, but is not limited to, applied to various advanced packaging processes.

[0036] An embodiment of the present application provides a slurry comprising inorganic particles and a liquid dispersion medium, wherein in the slurry, the ratio of the D50 particle size to the D90 particle size of the inorganic particles is greater than 0.5, the ratio of the mode diameter to the D90 particle size of the inorganic particles is greater than 0.55, and the D50 particle size of the inorganic particles is in the range of 0.25 μm-1.5 μm.

[0037] Among them, the word "mode diameter" is Mode Diameter in English, also known as "most frequent particle size". The mode diameter refers to the diameter of the particle with the highest frequency in the powder; specifically, it can be the particle size corresponding to the particle with the highest volume fraction in the powder, or the particle size corresponding to the highest frequency (i.e., the highest point) in the particle size distribution curve of the particle. In the particle size distribution curve of inorganic particles, the D50 particle size and the D90 particle size are the particle sizes corresponding to the cumulative volume distribution percentages of the inorganic particles reaching 50% and 90%, respectively. Among them, the D50 particle size can also be called the median particle size, etc. The particle size distribution curve of the above particles can be obtained based on the laser diffraction method, and the instrument used can be a particle size analyzer, etc.

[0038] The D50 particle size of the inorganic particles in the above-mentioned slurry is controlled within the above-mentioned size range, which is more suitable for application in the field of miniaturized electronic component packaging in the form of a slurry. However, the smaller the D50, the better. A suitable D50 is conducive to the slurry having low viscosity even when a large amount of small-particle inorganic particles are added; controlling the ratio of D50 to D90 to be greater than 0.5 can ensure that the particle size distribution of particles with a particle size above D90 is closer to D50, thereby reducing the sedimentation effect caused by large particles, and the slurry has good stability and is not easy to settle; controlling the ratio of mode diameter to D90 to be greater than 0.55 can make the mode diameter closer to D90, which is more conducive to appropriately reducing the viscosity of the slurry, thereby increasing the solid content of the slurry, and a higher solid content is also conducive to preventing particle sedimentation. Therefore, under the joint control of the above-mentioned parameter ranges, the slurry ultimately contains a large amount of well-dispersed inorganic particles while still having low viscosity and high fluidity. The subsequent addition of the slurry to the resin material for packaging materials can ensure that a resin composition with a high inorganic particle filling rate is obtained, and the thermal expansion coefficient of the cured product is low, thereby improving the warping problem caused by the packaging of electronic components and improving the packaging reliability.

[0039] Generally, when D50 is large, D90 is also correspondingly large. A suitably large D50 is conducive to reducing viscosity, but when D90 is large, particles are prone to sedimentation, so there is a contradiction. In the above-mentioned slurry provided by the present application, the ratio of D50 to D90 of the particles is greater than 0.5, and the ratio of the mode diameter to the D90 particle diameter is greater than 0.55, which can ensure that when D50 is constant, D90 is as small as possible, and the particle size distribution is concentrated closer to the smaller D90, which has characteristics that the existing slurry does not have. The above-mentioned slurry of the present application can be prepared by selecting a variety of inorganic particles with different median particle sizes as the solid component of the slurry, so that the D50 particle size, the ratio of the mode diameter to the D90 particle size of the inorganic particles in the final slurry are within the above-mentioned specific range, and the D50 particle size is within a specific size range; it can also be obtained by regulating the particle size distribution of the existing particle slurry.

[0040] Specifically, the D50 of the inorganic particles can be, for example, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.45 μm, etc. In some embodiments, the D50 of the inorganic particles is 0.4 μm-1.0 μm, and can further be 0.5 μm-0.9 μm, 0.6-1.0 μm, etc.

[0041] In some embodiments of the present application, in the above-mentioned slurry, the ratio of the D50 particle size to the D90 particle size of the inorganic particles can be in the range of 0.51-0.80, for example, specifically 0.52, 0.53, 0.54, 0.55, 0.56, 0.58, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65, 0.67, 0.68, 0.70, 0.72, 0.75, 0.78, 0.79, etc. The larger the ratio of D50 to D90 is than 0.5, the more concentrated the particle size distribution of the inorganic particles is, and the closer D90 is to D50, which is conducive to ensuring that there are fewer large particles in the slurry and the slurry is less likely to settle. In some embodiments, the ratio of D50 to D90 of the inorganic particles is 0.51-0.65.

[0042] In some embodiments of the present application, in the above slurry, the ratio of the mode diameter of the inorganic particles to the D90 particle diameter can be in the range of 0.56-0.85, for example, specifically 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65, 0.67, 0.68, 0.69, 0.70, 0.72, 0.75, 0.78, 0.80, 0.82, 0.84, etc. In this case, the closer the mode diameter is to the D90 particle diameter, the more obvious the effect of reducing the slurry viscosity and increasing the solid content is, while at the same time preventing an excessive number of large particles in the slurry, and the higher the storage stability of the slurry.

[0043] In the embodiment of the present application, in the above slurry, the D90 particle size of the inorganic particles may be in the range of 0.5 μm-2.5 μm, for example, 0.6 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 2.0 μm, 2.2 μm, 2.4 μm, etc. In some embodiments, the D90 of the inorganic particles is in the range of 0.8 μm-1.45 μm, and further in the range of 1.0-1.4 μm. Appropriate D90 particle size can ensure that there are not too many large inorganic particles in the slurry. At the same time, based on the above "the ratio of D50 to D90 is greater than 0.5, and the ratio of mode diameter to D90 is greater than 0.55", it can ensure that there are not too many small particles in the slurry. Proper control of particle size distribution is conducive to the slurry taking into account low sedimentation, high solid content and low viscosity.

[0044] In the embodiment of the present application, in the above-mentioned slurry, the mode diameter of the inorganic particles is in the range of 0.3μm-1.65μm, for example, specifically 0.35μm, 0.4μm, 0.458μm, 0.5μm, 0.6μm, 0.8μm, 0.9μm, 1.0μm, 1.1μm, 1.2μm, 1.3μm, 1.4μm, 1.5μm, 1.6μm, etc. In some embodiments, the mode diameter is in the range of 0.6-1.5μm, and can further be in the range of 0.6-1.2μm. An appropriate mode diameter can ensure that the particles with the largest amount in the slurry have a suitable particle size, and that particles of other particle sizes are compounded, and based on the above-mentioned "ratio of mode diameter to D90 is greater than 0.55", it can be ensured that there are not too many small particles in the slurry, and the large particle size will not deviate too much from the mode diameter, which is beneficial for the slurry to take into account low viscosity, high solid content and non-settling properties.

[0045] It is understood that the D90 particle size of the inorganic particles is greater than the D50 particle size and the mode diameter. In some embodiments, the inorganic particles have a D50 of 0.4 μm to 1.0 μm, a mode diameter of 0.5 μm to 1.2 μm, and a D90 of 0.8 μm to 1.45 μm. In other embodiments, the inorganic particles have a D50 of 0.5 μm to 0.9 μm, a mode diameter of 0.6 μm to 1.1 μm, and a D90 of 1.0 μm to 1.4 μm.

[0046] In the embodiment of the present application, the cut-off particle size of the inorganic particles is less than 5 μm, and further can be less than or equal to 3 μm, for example, specifically 2 μm, 2.5 μm, 3 μm, etc. Among them, the cut-off particle size, i.e., the cut-off particle size, the truncation particle size, is the theoretical maximum particle size, which can correspond to the size of the screen used for screening in the preparation of the slurry. The smaller cut-off particle size reflects that there are very few particles of extremely large particle size in the slurry, and the slurry is relatively difficult to settle. It should be noted that, due to the limitations of the screen itself and the influence of aspects such as slurry storage, it is inevitable that there may be some particles (such as ppm level) exceeding the cut-off particle size in the slurry.

[0047] In the embodiment of the present application, in the above slurry, the inorganic particles are m 2 The product of the specific surface area in μm and the D50 particle size of the inorganic particles in μm is in the range of 2.6-4.5, and the specific ratio can be 2.7, 2.8, 2.9, 3.0, 3.2, 3.5, 3.8, 4.0, 4.2, 4.4, etc. Controlling the specific surface area and D50 particle size of the particles to satisfy the above relationship helps to ensure that there are an appropriate number of small particles in the slurry, avoiding the presence of too many ultrafine particles that increase the slurry viscosity, and avoiding the presence of too many large particles that make the slurry easy to settle, thereby ensuring that the slurry viscosity is in an appropriately low range and is not prone to particle sedimentation, which is conducive to increasing the solid content. The specific surface area of ​​the inorganic particles can be measured by nitrogen adsorption method after removing the liquid dispersion medium in the slurry.

[0048] In the embodiment of the present application, in the above slurry, the specific surface area of ​​the inorganic particles is 3.1m 2 / g-8.0m 2 / g, for example, 3.2m 2 / g, 3.3m 2 / g, 3.5m 2 / g, 4.0m 2 / g, 4.5m 2 / g, 5.0m 2 / g, 5.5m 2 / g, 6.0m 2 / g, 7.0m 2 / g, 7.5m 2 / g, 7.8m 2 / g、8m 2 / g, etc. If the specific surface area of ​​the inorganic particles is too large, the powder dispersion is difficult, the slurry viscosity is high, and it is difficult to prepare a slurry with a high solid content; if the specific surface area is too small, the viscosity of the slurry is too low and it is easy to settle. Therefore, it is necessary to control the appropriate specific surface area, which helps to improve the above problems to a certain extent. In some embodiments, the specific surface area of ​​the inorganic particles is 3.5m 2 / g-7.0m 2 / g.

[0049] In the present application, the above-mentioned inorganic particles may be surface-modified or unmodified inorganic particles. In some embodiments of the present application, the surface of the inorganic particles may be modified with a surface modifier. The inorganic particles at this time may be referred to as surface-modified inorganic particles. The modification of the surface of the inorganic particles by the surface modifier is beneficial to improving the compatibility between the inorganic particles and the liquid dispersion medium such as an organic solvent, thereby reducing the sedimentation probability of the particles, improving their dispersion stability, and facilitating the preparation of a slurry with a high solid content. In an embodiment of the present application, the surface modifier includes an organosilicon compound. The organosilicon compound includes, but is not limited to, one or more of a silane coupling agent and a silazane. The organosilicon compound may be grafted onto the surface of the inorganic particle through chemical bonds and / or physical adsorption.

[0050] Silane coupling agents generally refer to compounds 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 alkoxysilanes, with a structural formula typically represented by Y-Si(R1)(R2)(R3), where at least one of R1, R2, and R3 is an alkoxy group, and Y represents an organic functional group that is reactive or compatible with organic matter. The alkoxy group attached to the Si atom is generally reactive with inorganic particles, decomposing upon exposure to water to form silanol groups (Si-OH). Si-OH can form chemical bonds or physical adsorption with polar groups such as -OH on the surface of inorganic particles through dehydration condensation.

[0051] In some embodiments of the present application, the silane coupling agent is a compound having at least one group selected from the group consisting of an alkyl group, a phenyl group, a vinyl group, an epoxy group, an amino group, and a (meth)acryloyloxy group. That is, the Y mentioned above contains an alkyl group, a phenyl group, a vinyl group, an epoxy group, an amino group, a (meth)acryloyloxy group, and the like. Amine groups include primary amino groups (i.e., -NH2) and secondary amino groups. (Meth)acryloyloxy groups specifically include acryloyloxy and methacryloyloxy groups.

[0052] For example, the silane coupling agent can be an alkoxysilane having an alkyl group, such as trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, and methyltrimethoxysilane; an alkoxysilane having a phenyl group, such as phenyldimethylmethoxysilane, phenyltrimethoxysilane, and phenethyltrimethoxysilane; an alkoxysilane having a vinyl group, such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltri(β-methoxyethoxy)silane; γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-(methacryloxy)silane; Alkoxysilanes having a (meth)acryloyloxy group, such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane; Alkoxysilanes having an epoxy group, such as N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.

[0053] Silazanes are substances in which two hydrogen atoms in ammonia are replaced by hydrocarbyl-containing silyl groups. For example, silazanes may include, but are not limited to, one or more of hexamethyldisilazane ([(CH3)3Si]2NH), tetramethyldiphenyldisilazane, and tetramethyldivinyldisilazane.

[0054] In the embodiment of the present application, the mass ratio of the surface modifier to the inorganic particles is: 2 When preparing surface-modified inorganic particles, this parameter range helps guide the preparation of a surface modifier with an appropriate amount of surface modification, thereby effectively improving the dispersion stability of the particles while not introducing too much surface modifier and reducing the particle content in the slurry.

[0055] In the embodiment of the present application, the inorganic particles include one or more of silicon dioxide, aluminum oxide, magnesium oxide, zinc oxide, aluminum nitride, silicon nitride, silicon carbide, barium sulfate, and calcium carbonate. The slurry of these inorganic particles is added to the resin material to reduce the thermal expansion coefficient of the resulting resin composition system, improve thermodynamic properties, and thus enhance the packaging reliability of the resin composition as an encapsulation material. In some embodiments, the inorganic particles are silicon dioxide particles. Using silicon dioxide particles is conducive to better reducing the thermal expansion coefficient of the resin composition, improving fluidity, etc.

[0056] In some embodiments of the present application, the inorganic particles are spherical particles with a sphericity greater than 98%. The use of spherical particles with a high sphericity is more conducive to improving the fluidity of the resin composition and enhancing its ability to fill narrow gaps. In other embodiments of the present application, the inorganic particles may also be non-spherical particles, such as cylindrical particles, cubic particles, or other irregularly shaped particles.

[0057] It should be noted that the above description of parameter ranges such as D50 particle size, D90 particle size, mode diameter, ratio of D50 to D90, ratio of mode diameter to D90, and product of specific surface area and D50 particle size in this application is applicable both to inorganic particles whose surfaces are modified with surface modifiers and to inorganic particles that are not modified with surface modifiers.

[0058] In the present application, by controlling parameters including but not limited to "the ratio of D50 to D90 particle size of the inorganic particles in the slurry is greater than 0.5, and the ratio of the mode diameter to D90 particle size is greater than 0.55", it can be ensured that when the mass proportion of the inorganic particles in the slurry is high, the viscosity of the slurry is low and the dispersion of the particles therein is good. In the embodiment of the present application, the mass percentage of the inorganic particles in the slurry is greater than or equal to 60wt%, and further greater than or equal to 70wt%. The inorganic particles may be particles whose surfaces are modified with a surface modifier, or particles that are not modified with a surface modifier. By controlling the inorganic particles in the slurry to a higher content, when the slurry is added to the resin material for the packaging material, the inorganic particles in the resulting resin composition can be made to have a higher mass proportion, less liquid dispersion medium is introduced, and the pressure for removing the liquid dispersion medium is reduced, which is more conducive to reducing the thermal expansion coefficient of the cured product of the resin composition, reducing thermal stress, and thus improving packaging reliability.

[0059] In some embodiments of the present application, the mass percentage of the inorganic particles in the slurry is 70-90wt%, for example, 70%, 72%, 73%, 75%, 78%, 80%, 82%, 85%, 88%, 89%, etc. By controlling the content of the inorganic particles within a relatively high range, and based on the range requirements for the ratio of D50 to D90 and the ratio of mode diameter to D90 of the inorganic particles as previously described in this application, it is possible to ensure that when the content of the inorganic particles in the slurry is relatively high, its dispersibility is better and the viscosity is lower, which in turn is conducive to the resin composition having low viscosity, good dispersibility, and a lower thermal expansion coefficient of its cured product.

[0060] In some embodiments of the present application, the liquid dispersion medium includes an organic solvent; wherein the relative dielectric constant of the organic solvent at 20°C is greater than 1 and less than 25. Controlling the dielectric properties of the organic solvent to meet this requirement helps to ensure good compatibility between the slurry containing the organic solvent and common resin materials (such as epoxy resins), thereby ensuring that the inorganic particles in the resin composition formed by the two have good dispersibility. In the embodiment of the present application, the organic solvent includes one or more of butanone, toluene, ethyl acetate, diethylene glycol ethyl ether acetate, and propylene glycol methyl ether acetate, but is not limited thereto. Different organic solvents can be selected according to the different application scenarios of the above-mentioned slurry.

[0061] In other embodiments of the present application, the liquid dispersion medium may include silicone oil, resin oligomers or monomers thereof, such as liquid epoxy resin oligomers or monomers, liquid acrylic resin oligomers or monomers, etc. The specific liquid dispersion medium may be selected according to different application scenarios.

[0062] In the present application, the slurry is a raw material required for preparing the resin composition. Therefore, in the embodiment of the present application, the slurry does not contain a curing agent.

[0063] In the embodiment of the present application, the preparation method of the above slurry may include:

[0064] Selecting inorganic particle powders with different median particle sizes and a single distribution, mixing the multiple inorganic particle powders, and adding a liquid dispersion medium so that the D50 particle size of the inorganic particles in the resulting slurry is within the range of 0.25 μm to 1.5 μm, the ratio of the D50 particle size to the D90 particle size of the inorganic particles is greater than 0.5, and the ratio of the mode diameter to the D90 particle size of the inorganic particles is greater than 0.55;

[0065] Alternatively, the particle size distribution of the initial slurry containing inorganic particles and a liquid dispersion medium is regulated so that the D50 particle size of the inorganic particles in the slurry obtained after regulation is in the range of 0.25 μm to 1.5 μm, the ratio of the D50 particle size to the D90 particle size of the inorganic particles is greater than 0.5, and the ratio of the mode diameter to the D90 particle size of the inorganic particles is greater than 0.55.

[0066] The preparation method of the slurry is simple and easy to operate, and can produce the slurry with the above-mentioned excellent properties. Among them, regarding the particle size parameter range of the inorganic particles in the final slurry, the selection range of the liquid dispersion medium, etc., please refer to the description above in this application.

[0067] In some embodiments of the present application, after mixing multiple inorganic particle powders with different median particle sizes, a surface modifier may be added for surface modification before adding the liquid dispersion medium. The addition of the surface modifier can improve the dispersibility of the mixed particles in the liquid dispersion medium. The selection range of the surface modifier can be found in the description above.

[0068] In other embodiments of the present application, the means for controlling the particle size distribution of the initial slurry may include, but is not limited to, one or more of fractional centrifugation, fractional filtration, static standing, or other optional means. Fractional centrifugation may include multiple centrifugations at different centrifugal speeds, such as initially performing a low-speed centrifugation followed by a high-speed centrifugation of the resulting supernatant. In some embodiments, the initial slurry further contains a surface modifier. This ensures better dispersibility of the inorganic particles in the slurry.

[0069] The embodiment of the present application further provides a resin composition, comprising a resin material and the above-mentioned slurry liquid of the embodiment of the present application.

[0070] In the resin composition formed by mixing the above-mentioned slurry and the resin material in the embodiment of the present application, the inorganic nanoparticles can be evenly dispersed in the liquid resin composition, the viscosity and fluidity of the resin composition are appropriate, and it can be smoothly coated and then formed into a coating with good morphology after curing, and it has strong applicability; at the same time, since the inorganic particles in the above-mentioned slurry have good dispersibility, high content and low slurry viscosity, the viscosity of the resin composition is low, and the filling rate of the inorganic particles in the resin composition can be relatively high, which can ensure that the cured product of the resin composition has a lower thermal expansion coefficient; in addition, when the slurry concentration is high, the liquid dispersion medium introduced into the resin composition is relatively small, which can reduce the pressure of removing the dispersion medium in the later stage, and is more conducive to the formulation design of the resin composition.

[0071] In some embodiments of the present application, the resin material includes epoxy resin, and the resin composition also includes a curing agent. Epoxy resin is a commonly used resin material in the field of semiconductor packaging. When heated, the epoxy resin and the curing agent can chemically react to form a cured product with a three-dimensional network structure.

[0072] Wherein, epoxy resin can comprise one or more in bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, aromatic epoxy resin (as naphthalene series epoxy resin, biphenyl type epoxy resin etc., aminophenol type epoxy resin,) etc.In resin combination, epoxy resin can be one, also can be multiple (that is, be greater than or equal to two) combination.Multiple epoxy resins are used in combination, resin combination can be made to obtain more excellent comprehensive properties, for example, can balance viscosity, bonding force etc.The curing agent that is suitable for epoxy resin can comprise one or more in acid anhydride curing agent, amine curing agent etc.Wherein, can be known the kind of epoxy resin and the kind of curing agent by the method analysis such as nuclear magnetic resonance spectrum, infrared spectrometer, elemental analysis.

[0073] It should be noted that when the liquid dispersion medium is a resin oligomer, the resin material in the resin composition is different from the resin oligomer serving as the liquid dispersion medium, and the molecular weight of the former is generally greater than that of the latter, thereby ensuring good thermodynamic properties of the resin composition.

[0074] In order to improve the performance of the resin composition, in some embodiments of the present application, the resin composition may further include an auxiliary agent, including but not limited to one or more of a coupling agent, a flow improver, a thickener, a flame retardant, a colorant, an ion trapping agent, a stress absorber, a curing accelerator, and a release agent. These auxiliary agents may be added according to specific needs.

[0075] The present application also provides the use of the above-mentioned slurry and the above-mentioned resin composition in the embodiments of the present application in the sealing packaging of electronic components.

[0076] Above-mentioned slurry, above-mentioned resin combination can be used as electronic packaging material in electronic component sealing package.Wherein, above-mentioned resin combination is liquid packaging material, can be formed film layer etc. after coating / filling, solidification.Above-mentioned slurry can be used as a kind of preparation raw material of this resin combination.In the embodiment of the present application, electronic component can be chip, transistor (such as diode, triode), LED, resistance-capacitance-sensing element (such as resistor, capacitor, inductor) etc.Wherein, the form of encapsulation includes but is not limited to ball grid array (Ball Grid Array, BGA) encapsulation, flip chip (Flip chip) encapsulation, system-level package (Systemin Package), four-sided flat package (Quad Flat Package, QFP), stacked package (package-on-package) and other packaging structures.

[0077] In the embodiment of the present application, the application of the above-mentioned slurry and the above-mentioned resin composition in the sealed packaging of electronic components can specifically include: making at least one of the core board of the packaging substrate, the build-up film of the packaging substrate, the solder mask ink layer on the packaging substrate, and the adhesive layer for fixing electronic components (such as chip adhesive film, such as bottom filling adhesive layer), but is not limited to this.

[0078] The present application also provides an electronic packaging material for sealing electronic components. The packaging material comprises the resin composition provided in the embodiments of the present application and / or a cured product of the resin composition. Using the resin composition provided in the embodiments of the present application as a packaging material for electronic component packaging can enhance the packaging effect and improve the service reliability of the electronic components.

[0079] As described above in this application, the application of the resin composition in the sealed packaging of electronic components may include one or more of the core board for making a packaging substrate, a build-up film for a packaging substrate, a solder resist ink layer on a packaging substrate, an adhesive layer for fixing electronic components (such as a chip bonding film, such as a bottom filling layer), etc.; accordingly, the core board, build-up film, solder resist ink layer and adhesive layer for fixing electronic components of the packaging substrate may contain a cured product of the resin composition.

[0080] The present application also provides a cured product obtained by curing the resin composition described in the present application. Specifically, the cured product comprises a cured product of the resin composition described in the present application. The cured product may be in the form of a film, a sheet, a three-dimensional structure, or the like. The cured product has properties such as a low coefficient of thermal expansion (CTE), a high glass transition temperature (Tg), high mechanical strength, and low water absorption, and can be used as a packaging material for encapsulating electronic components.

[0081] The embodiment of the present application also provides a sealed package, including the solidified material described above in the embodiment of the present application.

[0082] See also Figure 1 , Figure 1A schematic structural diagram of a sealed package 100 provided for one embodiment of the present application. The sealed package 100 may be an electronic device package, and may further be a semiconductor package, a chip package, and the like. Specifically, the sealed package 100 includes a packaging substrate 10 and an electronic component 20 arranged on the packaging substrate 10. The packaging substrate 10 includes a core board 11 and a build-up film 12 and a solder mask ink layer 13 sequentially stacked on opposite sides of the core board 11. At least one of the core board 11, the build-up film 12, and the solder mask ink layer 13 includes a cured product of the above-mentioned resin composition of the present application. The electronic component 20 may be various components that need to be packaged, including but not limited to one or more of chips, transistors (such as diodes, triodes), LEDs, resistors, capacitors, and inductors (such as resistors, capacitors, and inductors). When the electronic component 20 is a chip, the sealed package 100 is a chip package. The present application will hereinafter be specifically described using the example of the electronic component 20 being a chip.

[0083] In some embodiments of the present application, the electronic component 20 includes a chip; at least one (ie, one or more) chips are provided on the package substrate 10. Figure 1 , Figure 1 A plurality of stacked chips are provided on the package substrate 10, which can be respectively named as chip 20a, chip 20b, and chip 20c. Chip 20a is close to the package substrate 10. Chip 20a, chip 20b, and chip 20c can each be electrically connected to the package substrate 10 through leads. Die bonding films 30 are provided between chip 20a and the package substrate 10, and between adjacent stacked chips (i.e., between chip 20a and chip 20b, and between chip 20b and chip 20c). At least one of these die bonding films 30 can include a cured product of the resin composition described above.

[0084] It is understandable that in other embodiments of the present application, when a chip (such as chip 20a) is provided on the packaging substrate 10, the chip 20a is attached to the packaging substrate 10 via a chip bonding film, and the chip bonding film includes the cured product of the above-mentioned resin composition of the present application. In some other embodiments of the present application, a plurality of chips are provided on the packaging substrate 10 in direct contact with the packaging substrate 10 (here, "direct contact" means that there are no other chips between the packaging substrate 10 and the chip), and a chip bonding film containing the cured product of the above-mentioned resin composition can be provided between these chips and the packaging substrate 10.

[0085] In addition, it should be noted that Figure 1 The packaging substrate 10 may also have electronic components (such as chips) attached thereto by other means (such as welding). In this case, the electronic components are attached to the substrate by setting multiple welding bumps on the side facing the packaging substrate 10.

[0086] Figure 1 In the embodiment, the package substrate 10 has a plurality of solder balls 14 (such as tin balls) arranged in an array on one side away from the electronic components 20, and the package substrate 10 can be soldered to the circuit board through the solder balls 14 (see Figure 2 ), the electronic components 20 in the sealed package 100 can be electrically connected to the circuit board 202 by means of a conductive structure (not shown) penetrating the substrate, solder balls 14, etc. Figure 1 The sealed package 100 is called a BGA package. It is understandable that the chip package can also be a package of other packaging forms such as FC-CSP (Flip Chip-Chip Scale Package) and System in Package.

[0087] The sealed package 100 of the embodiment of the present application uses the resin composition provided in the embodiment of the present application to encapsulate electronic components, and has high process operability and high packaging reliability.

[0088] An embodiment of the present application further provides an electronic device, which includes the sealed package 100 provided in the embodiment of the present application.

[0089] Among them, electronic devices can include various consumer electronic products, such as mobile phones, tablet computers, laptops, portable computers, wearable devices (such as smart bracelets, smart watches, smart helmets, smart glasses, etc.), vehicle-mounted equipment, home entertainment equipment (such as televisions, DVD players, video recorders, camcorders, radios, recorders, stereo systems, record players, laser record players, etc.), home office equipment (such as scanners, microphones, etc.), home electronic health care equipment, or other devices connected to wireless modems, etc. The electronic device can also be a mobile device such as a car, or an energy storage device, etc., which is not limited in the embodiments of the present application.

[0090] In some embodiments, see Figure 3 The electronic device 200 provided in the embodiment of the present application includes a housing 201, a circuit board 202 and a sealed package 100 ( Figure 3 (not shown in the figure), inside the electronic device 200, the sealed package 100 may be as follows Figure 2 It is shown disposed on the circuit board 202 and electrically connected to the circuit board 202. In some embodiments, the housing 201 may include a front cover assembled on the front side of the electronic device and a rear shell assembled on the rear side, and the circuit board 202 may be fixed inside the rear shell. Figure 3 The electronic device 200 shown may specifically be a mobile phone or the like.

[0091] The embodiments of the present application are further described below with reference to a number of embodiments.

[0092] Example 1

[0093] An inorganic particle slurry comprises the following components in the following mass proportions: 75 wt% of inorganic particles (specifically, silica particles whose surfaces are modified with N-phenyl-3-aminopropyltrimethoxysilane (KBM-573)), and 25 wt% of butanone. The inorganic particles have a D50 particle size of 0.75 μm, a D90 particle size of 1.35 μm, a mode diameter of 0.9 μm, a D50 to D90 ratio of 0.556, and a mode diameter to D90 ratio of 0.667; and a specific area of ​​the inorganic particles of 4.8 m 2 / g.

[0094] The preparation method of the slurry comprises: selecting silicon dioxide powders with different median particle sizes, compounding the multiple silicon dioxide powders, and characterizing the particle size distribution of the compounded particles using a laser particle size meter. Figure 4 As shown in the figure, the D50 particle size of the composite particles was measured to be 0.75 μm, the D90 was 1.35 μm, and the mode diameter was 0.9 μm; and the specific surface area SSA of the composite particles was measured by nitrogen adsorption specific surface area analyzer to be 4.8 m 2 / g. Afterwards, 792.8g of the composite particles were weighed, and 7.2g of the surface modifier KBM-573 was added under high-speed stirring. The mixture was mixed evenly to obtain surface-modified particles. 800g of the surface-modified particles were then mixed with 257.07g of butanone, and mechanically dispersed using a sand mill or high-speed shearing equipment. The oversized particles were then filtered to remove the slurry, thereby obtaining a silica butanone slurry with a solid content of 75%. The particle size parameters of the particles in the slurry, such as D50 particle size, D90 particle size, and mode diameter, can be obtained by testing the slurry with a laser particle size analyzer. The specific surface area of ​​the particles can be measured using a nitrogen adsorption specific surface area analyzer after removing the butanone solvent from the slurry.

[0095] In addition, following the above method, slurries with inorganic particle contents of 70 wt%, 80 wt%, and 85 wt% were prepared to investigate whether hard precipitates appeared at the bottom of the slurries with different viscosities after standing for a certain number of days.

[0096] Example 2

[0097] The preparation of an inorganic particle slurry comprises: selecting commercially available silica powder, measuring the particle size parameters of the powder using a laser particle size analyzer as follows: D50 particle size is 0.68 μm, D90 is 1.42 μm, and mode diameter is 0.77 μm; using a nitrogen adsorption specific surface area analyzer to measure the specific surface area (SSA) of the above powder to be 7.2 m 2 / g. After that, 792g of the above powder was weighed, and 8g of surface modifier KBM-573 was added under high-speed stirring. After mixing evenly, surface-modified particles were obtained. Then, the particle size distribution of the surface-modified particles was regulated (the particle size distribution before and after regulation is shown in the figure). Figure 5 The specific process is as follows: the modified particles are first dispersed in butanone to obtain a mixture with a solid content of 53 wt%. The mixture is then allowed to settle freely. Samples are taken from the upper and lower portions at various intervals and the particle sizes are analyzed using a laser particle size analyzer. The upper supernatant and a portion of the upper slurry containing ultrafine particles smaller than 250 nm are removed. The intermediate suspension slurry is then removed, and the bottom sediment is removed to remove particles larger than 2.5 μm. The final slurry has a solid content of 70 wt%.

[0098] Among them, the slurry of Example 2 with a solid content of 70wt% was measured by a laser particle size analyzer. The D50 particle size of the particles in the slurry was 0.68μm, the D90 particle size was 1.30μm, the mode diameter was 0.77μm, the ratio of D50 to D90 was 0.523, and the ratio of mode diameter to D90 was 0.592. After removing the butanone solvent from the slurry, the specific surface area of ​​the inorganic particles was measured by a nitrogen adsorption specific surface area analyzer and was 6.0m 2 / g.

[0099] Example 3

[0100] An inorganic particle slurry is prepared, comprising: a powder and its surface modification treatment as described in Example 2. The particle size distribution of the surface-modified particles is controlled by first dispersing the modified particles in toluene to obtain a mixture with a solids content of 53 wt%. Unwanted particles are then removed by fractional centrifugation, initially at a low speed to remove particles larger than 2.5 μm at the bottom, followed by a high-speed centrifugation to remove the supernatant and particles smaller than 250 nm. The lower layer obtained after high-speed centrifugation is then dispersed in toluene to obtain a slurry with a solids content of 76 wt%.

[0101] Among them, the slurry of Example 3 with a solid content of 76wt% was measured by a laser particle size analyzer. The D50 particle size of the particles in the slurry was 0.66μm, the D90 particle size was 1.20μm, and the mode diameter was 0.75μm. Among them, the ratio of D50 to D90 was 0.55, and the ratio of mode diameter to D90 was 0.625. After removing the toluene solvent from the slurry, the specific surface area of ​​the inorganic particles was measured by a nitrogen adsorption specific surface area analyzer and was 5.8m 2 / g.

[0102] Example 4

[0103] An inorganic particle slurry was prepared. The powder selection and particle size formulation were the same as in Example 1. The surface modification of the powder differed primarily from Example 1 in that 3-glycidylpropyltrimethoxysilane (KBM-403) was used as a surface modifier. Specifically, 795.7 g of the formulated powder was weighed and mixed with 4.3 g of 3-glycidylpropyltrimethoxysilane (KBM-403) and 233.38 g of butanone under high-speed stirring. The mixture was then mechanically dispersed using a sand mill and filtered to remove oversized particles, yielding a silica butanone slurry with a solids content of 77%.

[0104] In the slurry provided in Example 4, the inorganic particles are silica particles whose surfaces are modified with KBM-403, with a content of 77 wt%, and the rest is 23 wt% of butanone, wherein the D50 particle size of the inorganic particles in the slurry is 0.73 μm, the D90 particle size is 1.32 μm, and the mode diameter is 0.85 μm, wherein the ratio of D50 to D90 is 0.553, and the ratio of mode diameter to D90 is 0.644; the specific area of ​​the inorganic particles is 4.9 m 2 / g.

[0105] Example 5

[0106] A slurry comprises the following components in proportion by weight: 80 wt% of inorganic particles (specifically, spherical silica particles whose surfaces are modified with 0.7 wt% of KBM-573), and 20 wt% of butanone; wherein the inorganic particles have a D50 particle size of 0.85 μm, a D90 particle size of 1.38 μm, and a mode diameter of 0.97 μm, wherein the ratio of D50 to D90 is 0.616, and the ratio of mode diameter to D90 is 0.703; and the specific area of ​​the inorganic particles is 4.2 m 2 / g.

[0107] Example 6

[0108] A slurry comprises the following components in proportion by weight: 82 wt% of inorganic particles (specifically, spherical silica particles whose surfaces are modified with 0.5 wt% of KBM-1003 (vinyltrimethoxysilane)), and 20 wt% of butanone; wherein the inorganic particles have a D50 particle size of 0.94 μm, a D90 particle size of 1.42 μm, and a mode diameter of 1.09 μm, wherein the ratio of D50 to D90 is 0.662, and the ratio of mode diameter to D90 is 0.768; and the specific area of ​​the inorganic particles is 3.5 m 2 / g.

[0109] Example 7

[0110] A slurry comprises the following components in proportion by weight: 83 wt% of inorganic particles (specifically, spherical silica particles whose surfaces are modified with 0.5 wt% of KBM-573), and 17 wt% of butanone; wherein the inorganic particles have a D50 particle size of 1.01 μm, a D90 particle size of 1.52 μm, and a mode diameter of 1.12 μm, wherein the ratio of D50 to D90 is 0.664, and the ratio of mode diameter to D90 is 0.737; and the specific area of ​​the inorganic particles is 3.2 m 2 / g.

[0111] Example 8

[0112] A slurry comprises the following components in proportion by weight: 70 wt% of inorganic particles (specifically, spherical silica particles whose surfaces are modified with 0.9 wt% of KBM-573), and 30 wt% of butanone; wherein the inorganic particles have a D50 particle size of 0.38 μm, a D90 particle size of 0.52 μm, and a mode diameter of 0.41 μm, wherein the ratio of D50 to D90 is 0.731, and the ratio of mode diameter to D90 is 0.788; and the specific area of ​​the inorganic particles is 6.9 m 2 / g.

[0113] Example 9

[0114] A slurry comprises the following components in proportion by weight: 85 wt% of inorganic particles (specifically, spherical silica particles whose surfaces are modified with 0.5 wt% of KBM-573), and 15 wt% of butanone; wherein the inorganic particles have a D50 particle size of 1.3 μm, a D90 particle size of 2.15 μm, and a mode diameter of 1.48 μm, wherein the ratio of D50 to D90 is 0.605, and the ratio of mode diameter to D90 is 0.688; and the specific area of ​​the inorganic particles is 3.1 m 2 / g.

[0115] In order to highlight the beneficial effects of the embodiments of the present application, the following comparative examples are provided.

[0116] Comparative Example 1

[0117] A slurry comprises the following components in proportion by weight: 70 wt% of inorganic particles (specifically, spherical silica particles whose surfaces are modified with 0.5 wt% of KBM-573), and 30 wt% of butanone; wherein the inorganic particles have a D50 particle size of 1.78 μm, a D90 particle size of 4.3 μm, and a mode diameter of 1.97 μm, wherein the ratio of D50 to D90 is 0.414, and the ratio of mode diameter to D90 is 0.458; and the specific area of ​​the inorganic particles is 4.5 m 2 / g.

[0118] Comparative Example 2

[0119] A slurry comprises the following components in proportion by weight: 70 wt% of inorganic particles (specifically, spherical silica particles whose surfaces are modified with 0.5 wt% of KBM-573) and 30 wt% of butanone; wherein the inorganic particles have a D50 particle size of 2.48 μm, a D90 particle size of 5.9 μm, and a mode diameter of 3.25 μm, wherein the ratio of D50 to D90 is 0.42, and the ratio of mode diameter to D90 is 0.55; and the specific area of ​​the inorganic particles is 2.6 m 2 / g.

[0120] Comparative Example 3

[0121] A slurry comprises the following components in proportion by weight: 50 wt% of inorganic particles (specifically, spherical silica particles whose surfaces are modified with 3 wt% of KBM-573), and 50 wt% of butanone; wherein the inorganic particles have a D50 particle size of 0.1 μm, a D90 particle size of 0.38 μm, and a mode diameter of 0.12 μm, wherein the ratio of D50 to D90 is 0.263, and the ratio of mode diameter to D90 is 0.316; and the specific area of ​​the inorganic particles is 30 m 2 / g.

[0122] Comparative Example 4

[0123] A slurry comprises the following components in proportion by weight: 70 wt% of inorganic particles (specifically, spherical silica particles whose surfaces are modified with 1 wt% of KBM-573), and 30 wt% of butanone; wherein the inorganic particles have a D50 particle size of 0.69 μm, a D90 particle size of 1.45 μm, a mode diameter of 0.77 μm, a D50 to D90 ratio of 0.476, and a mode diameter to D90 ratio of 0.531; and a specific area of ​​the inorganic particles of 7.2 m 2 / g.

[0124] In addition, the present application also provides slurries with inorganic particle contents of 75 wt%, 80 wt%, and 85 wt%, respectively, to investigate the number of days it takes for hard sediment to appear at the bottom of slurries with different viscosities after standing for a certain period of time.

[0125] Comparative Example 5

[0126] A slurry comprises the following components in proportion by weight: 70 wt% of inorganic particles (specifically, spherical silica particles whose surfaces are modified with 0.6 wt% of KBM-573), and 30 wt% of butanone; wherein the inorganic particles have a D50 particle size of 0.45 μm, a D90 particle size of 1.56 μm, a mode diameter of 0.87 μm, a D50 to D90 ratio of 0.288, and a mode diameter to D90 ratio of 0.558; and a specific area of ​​the inorganic particles of 6.3 m 2 / g.

[0127] Comparative Example 6

[0128] A slurry comprises the following components in proportion by weight: 70 wt% of inorganic particles (specifically, spherical silica particles whose surfaces are modified with 0.8 wt% of KBM-573), and 30 wt% of butanone; wherein the inorganic particles have a D50 particle size of 0.83 μm, a D90 particle size of 1.63 μm, a mode diameter of 0.88 μm, a D50 to D90 ratio of 0.509, and a mode diameter to D90 ratio of 0.540; and a specific area of ​​the inorganic particles of 4.3 m 2 / g.

[0129] Table 1 below summarizes the D50 particle size, D50 / D90, and mode diameter / D50 of the inorganic particles in the slurries of the Examples and Comparative Examples. Table 1 also summarizes the inorganic particle content in each slurry, the room temperature (25°C) viscosity of the slurry, and the number of days after each slurry was allowed to stand for a period of time before a hard precipitate formed on the bottom.

[0130] Table 1

[0131]

[0132] As can be seen from Table 1, the D50 particle size of the inorganic particles in the slurries of Comparative Examples 1-2 is too large, and D90 is also correspondingly too large. The slurries are very easy to settle after being placed. After standing for less than 2 days, there is an obvious hard precipitate, and it is difficult to disperse it again. The particle size of the inorganic particles in Comparative Example 3 is relatively small, which will make the viscosity of the slurry too large, making it difficult to prepare a slurry with a high solid content. Although the D50 of the inorganic particles in the multiple groups of slurries in Comparative Example 4 is within the range defined in this application (D50 is close to that of the slurry in Example 1, and there are also slurries with a viscosity close to that of Example 1), the ratio of its D50 to D90 and the ratio of its mode diameter to D90 are all too small, indicating that the particle size of the large particles is relatively large and the slurry is easy to settle. Therefore, hard precipitates appear after the slurries of various concentrations are left standing for less than 15 days. When the addition amount of inorganic particles reaches 85%, the system agglomerates and is no longer in the form of a slurry, which is not convenient for application, and the 85% is no longer the actual solid content. Although the D50 of the inorganic particles in the slurry of Comparative Examples 5-6 is within the range defined in this application, the ratio of their D50 to D90 or the ratio of their mode diameter to D90 is not within the range defined in this application, and hard precipitates appear at the bottom of the slurry after standing for 6 days.

[0133] The inorganic particle slurries of Examples 1-9 of the present application, by controlling the D50 of the particles within a specific size range, and controlling the ratio of D50 to D90 to be greater than 0.5, and the ratio of the mode diameter to D90 to be greater than 0.55, can ensure that no hard precipitate appears at the bottom of the slurry after 15 days of storage, and have good anti-sedimentation properties. At the same time, the slurry also has high solid content and low viscosity characteristics, thereby ensuring that the resin composition prepared using the slurry provided in the examples of the present application can obtain low viscosity, good fluidity and dispersibility, and the thermal expansion coefficient of the cured product is low.

[0134] It should be understood that the first, second and various numerical numbers involved in this document are only distinguished for the convenience of description and are not intended to limit the scope of this application.

[0135] In this application, "and / or" describes the relationship between related objects, indicating that three possible relationships exist. For example, "A and / or B" can mean: A exists alone, A and B exist simultaneously, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the related objects are in an "or" relationship.

[0136] In this application, "at least one" means one or more, and "more than one" means greater than or equal to two. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0137] The above merely represents several exemplary embodiments of the present application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present application. It should be noted that a person of ordinary skill in the art would be able to make various modifications and improvements without departing from the spirit of the present application, and these modifications and improvements fall within the scope of protection of the present application. Therefore, the scope of protection of the present application shall be determined by the appended claims.

Claims

1. A slurry, characterized in that: The slurry comprises inorganic particles and a liquid dispersion medium. In the slurry, the D50 particle size of the inorganic particles is in the range of 0.25 μm-1.5 μm, the ratio of the D50 particle size to the D90 particle size of the inorganic particles is greater than 0.5, and the ratio of the mode diameter to the D90 particle size of the inorganic particles is greater than 0.

55.

2. The slurry according to claim 1, characterized in that In the slurry, the ratio of D50 particle size to D90 particle size of the inorganic particles is in the range of 0.51-0.

80.

3. The slurry according to claim 1 or 2, characterized in that In the slurry, the ratio of the mode diameter of the inorganic particles to the D90 particle diameter is in the range of 0.56-0.

85.

4. The slurry according to any one of claims 1 to 3, characterized in that The mode diameter of the inorganic particles is in the range of 0.3 μm to 1.65 μm.

5. The slurry according to any one of claims 1 to 4, characterized in that The D90 particle size of the inorganic particles is in the range of 0.5 μm-2.5 μm.

6. The slurry according to any one of claims 1 to 5, characterized in that The cut-off particle size of the inorganic particles is less than 5 μm.

7. The slurry according to any one of claims 1 to 6, characterized in that The inorganic particles are measured in m 2 The product of the specific surface area in μm and the D50 particle size of the inorganic particles in μm is in the range of 2.6-4.

5.

8. The slurry according to claim 7, characterized in that The specific surface area of ​​the inorganic particles is 3.1 m 2 / g-8.0m 2 / g.

9. The slurry according to any one of claims 1 to 8, characterized in that The mass percentage of the inorganic particles in the slurry is greater than or equal to 60wt%.

10. The slurry according to claim 9, characterized in that The mass percentage of the inorganic particles in the slurry is 70-90wt%.

11. The slurry according to any one of claims 1 to 10, characterized in that: The surfaces of the inorganic particles are modified with a surface modifier; wherein the surface modifier includes one or more of a silane coupling agent and a silazane.

12. The slurry according to claim 11, characterized in that The mass ratio of the surface modifier to the inorganic particles is the mass ratio of the inorganic particles in m 2 / g is 0.0004-0.003 times the specific surface area.

13. The slurry according to claim 11, characterized in that The silane coupling agent has at least one group selected from the group consisting of an alkyl group, a phenyl group, a vinyl group, an epoxy group, an amino group, and a (meth)acryloxy group; the silazane includes one or more selected from the group consisting of hexamethyldisilazane, tetramethyldiphenyldisilazane, and tetramethyldivinyldisilazane.

14. The slurry according to any one of claims 1 to 13, characterized in that The inorganic particles include one or more of silicon dioxide, aluminum oxide, magnesium oxide, zinc oxide, aluminum nitride, silicon nitride, silicon carbide, barium sulfate, and calcium carbonate.

15. The slurry according to any one of claims 1 to 14, characterized in that The liquid dispersion medium includes an organic solvent, and the relative dielectric constant of the organic solvent at 20° C. is greater than 1 and less than 25.

16. The slurry according to claim 15, characterized in that The organic solvent includes one or more of butanone, toluene, ethyl acetate, diethylene glycol ethyl ether acetate, and propylene glycol methyl ether acetate.

17. A resin composition, characterized in that The invention comprises a resin material and the slurry according to any one of claims 1 to 16.

18. The resin composition according to claim 17, characterized in that The resin material includes epoxy resin, and the resin composition further includes a curing agent.

19. Use of the slurry according to any one of claims 1 to 16 and the resin composition according to any one of claims 17 to 18 in sealing and packaging electronic components.

20. The use according to claim 19, characterized in that The application in the sealed packaging of electronic components includes making at least one of a core board for a packaging substrate, a build-up film for a packaging substrate, a solder resist ink layer on a packaging substrate, and an adhesive layer for fixing electronic components.

21. A packaging material for sealing and packaging electronic components, characterized in that: The packaging material comprises the resin composition according to any one of claims 17 to 18 and / or a cured product of the resin composition.

22. A sealed package, characterized in that: The sealed package comprises a cured product of the resin composition according to any one of claims 17 to 18.

23. The sealed package according to claim 22, wherein: The sealed package includes a packaging substrate and electronic components arranged on the packaging substrate, the packaging substrate includes a core board and a build-up film and a solder resist ink layer stacked in sequence on opposite sides of the core board, wherein at least one of the core board, the build-up film, and the solder resist ink layer includes the solidified material.

24. The sealed package according to claim 23, wherein: The electronic component is a chip, at least one chip is arranged on the packaging substrate, and the chip bonding film arranged between the chip and the packaging substrate and / or between adjacent chips includes the cured product.

25. An electronic device, characterized in that: The electronic device comprises a circuit board and a sealed package as claimed in any one of claims 22 to 24 arranged on the circuit board.

26. A method for preparing a slurry, characterized in that: include: Selecting inorganic particle powders with different median particle sizes and single distribution, mixing a plurality of the inorganic particle powders, and adding a liquid dispersion medium, so that the D50 particle size of the inorganic particles in the obtained slurry is in the range of 0.25 μm-1.5 μm, the ratio of the D50 particle size to the D90 particle size of the inorganic particles is greater than 0.5, and the ratio of the mode diameter to the D90 particle size of the inorganic particles is greater than 0.55; Alternatively, the particle size distribution of the initial slurry containing inorganic particles and a liquid dispersion medium is regulated so that the D50 particle size of the inorganic particles in the slurry obtained after regulation is in the range of 0.25 μm-1.5 μm, the ratio of the D50 particle size to the D90 particle size of the inorganic particles is greater than 0.5, and the ratio of the mode diameter of the inorganic particles to the D90 particle size is greater than 0.55.

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