Silica dispersion, method for producing the same, resin composition, and use thereof

Abstract

The application relates to a silica dispersion, a preparation method thereof, a resin composition and application of the silica dispersion. The silica dispersion comprises the following components in parts by mass: 50-80 parts of silica, 0.2-1 part of a wetting agent, 0.3-1 part of a silane coupling agent, 0.5-2 parts of a dispersing agent and 16-49 parts of a solvent. The wetting agent is at least one selected from a polyether modified double structure polysiloxane wetting agent and a polyether modified hydroxyl-containing polydimethylsiloxane wetting agent, and the mass ratio of the wetting agent to the silica is 1:(100-160). The silica dispersion has the advantages that the silica is reacted with the specific wetting agent, and is further reacted with the silane coupling agent and the dispersing agent, and the proportion among the components is controlled, especially the addition amount of the wetting agent, so that the silica dispersion has a high solid content, good dispersibility, can be stably placed for more than 280 days, has a small particle size change and good storage stability.

Description

Technical Field

[0001] This application relates to the field of materials technology, and in particular to a silica dispersion and its preparation method, a resin composition and its application. Background Technology

[0002] As integrated circuits evolve towards miniaturization and high performance, flexible, thin substrates are widely used. These thin substrates are primarily composed of resin compositions, incorporating various materials such as metals, dielectrics, and composites. Due to differences in the coefficient of thermal expansion (CTE) of these materials, board warping is common. Therefore, high-filler silica, especially silica with a D50 < 5 μm, is often added to the resin composition to reduce CTE differences. However, small-particle-size silica, due to its large specific surface area, tends to agglomerate in the resin system. Traditional methods involve surface-modifying the silica to create a slurry before adding it to the resin composition; however, traditional silica slurries suffer from low solids content and poor storage stability.

[0003] Therefore, it is of great significance to provide a silica dispersion with high solid content and good storage stability. Summary of the Invention

[0004] Based on this, this application provides a silica dispersion with high solid content and good storage stability, its preparation method, resin composition and its application.

[0005] The technical solution to the above-mentioned technical problems in this application is as follows.

[0006] A silica dispersion, comprising the following components by mass parts:

[0007]

[0008] The wetting agent is selected from at least one of polyether-modified twin-structure polysiloxane wetting agent and polyether-modified hydroxyl-containing polydimethylsiloxane wetting agent, and the mass ratio of the wetting agent to the silica is 1:(100-160).

[0009] In some embodiments, the wetting agent in the silica dispersion is selected from at least one of TEGO Twin4000, LD-8400, RianPont2504, 8530H, and BYK-377.

[0010] In some embodiments, the silane coupling agent in the silica dispersion is selected from at least one of epoxy silane coupling agents, amino silane coupling agents, vinyl silane coupling agents, acrylate-based silane coupling agents, and isocyanate-based silane coupling agents.

[0011] In some embodiments, the silane coupling agent in the silica dispersion is selected from at least one of KBE-1003 and KBE-403.

[0012] In some embodiments, the dispersant in the silica dispersion is selected from at least one of polyether dispersants, polyester dispersants, polyurethane dispersants, polyacrylate dispersants, polyamide dispersants, and polyphosphate dispersants.

[0013] In some embodiments, the dispersant in the silica dispersion is selected from at least one of TEGO Dispers 670 and BYK DISPERBYK-2055.

[0014] In some embodiments, the solvent in the silica dispersion is selected from at least one of butanone, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, toluene, xylene, and N,N-dimethylformamide.

[0015] In some embodiments, the silica dispersion has a silica particle size of 0.5 μm to 25 μm.

[0016] This application provides a method for preparing a silica dispersion, comprising the following steps:

[0017] Raw materials are provided according to the composition of the silica dispersion described above;

[0018] The wetting agent, silane coupling agent, solvent and silica are mixed and stirred for the first time to obtain the first slurry; the first stirring time is 20 min to 40 min.

[0019] The first slurry and the dispersant are mixed and then stirred a second time to obtain a second slurry; the sum of the first stirring time and the second stirring time is 65 min to 125 min.

[0020] The second slurry is milled to obtain a silica dispersion; the milling time is 45 min to 180 min and the feed flow rate is 0.8 L / min to 3 L / min.

[0021] This application provides a resin composition comprising the above-described silica dispersion.

[0022] This application provides the use of the above-described resin composition in the preparation of integrated circuit substrates.

[0023] Compared with the prior art, the silica dispersion of this application has the following beneficial effects:

[0024] The aforementioned silica dispersion, through the use of specific types of wetting agents to interact with silica, and further interaction with silane coupling agents and dispersants, as well as the control of the proportions between the components, especially the amount of wetting agent added, results in a high solid content of silica dispersion, which can reach up to 83.5%; and good dispersibility, which allows it to be stored stably for more than 280 days with minimal particle size change and good storage stability. Detailed Implementation

[0025] The technical solution of this application will be further described in detail below with reference to specific embodiments. This application can be implemented in many different forms and is not limited to the embodiments described herein. It should be understood that the purpose of providing these embodiments is to make the disclosure of this application more thorough and comprehensive.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0027] In the description of this application, it should be understood that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, "multiple" means two or more, unless otherwise explicitly specified.

[0028] The weights of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the weights mentioned in the embodiments of this application can be well-known units of mass in the chemical industry, such as μg, mg, g, and kg.

[0029] One embodiment of this application provides a silica dispersion, comprising the following components by mass parts:

[0030]

[0031] The wetting agent is selected from at least one of polyether-modified twin-structure polysiloxane wetting agent and polyether-modified hydroxyl-containing polydimethylsiloxane wetting agent, and the mass ratio of the wetting agent to silica is 1:(100-160).

[0032] By using specific types of wetting agents to react with silica, and further reacting with silane coupling agents and dispersants, as well as controlling the proportions between the components, especially the amount of wetting agent added, the silica dispersion has a high solid content, reaching 83.5%; and good dispersibility, can be stably stored for more than 280 days, with little change in particle size and good storage stability.

[0033] It is understood that the parts of silica include, but are not limited to, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 65 parts, 70 parts, 75 parts, and 80 parts; the parts of wetting agent include, but are not limited to, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, and 1 part; the parts of silane coupling agent include, but are not limited to, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, and 1 part; and the parts of dispersant include, but are not limited to, 0.5 parts, 0.6 parts, 0.7 parts, and 0.8 parts. The quantities of solvent are as follows: 0.8 parts, 0.9 parts, 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts; the quantities of solvent are including but not limited to 16 parts, 16.5 parts, 18 parts, 20 parts, 21.5 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 49 parts; the mass ratio of wetting agent to silica is including but not limited to 1:100, 1:110, 1:115, 1:120, 1:125, 1:130, 1:135, 1:140, 1:150, 1:155, 1:160.

[0034] Another embodiment of this application provides a silica dispersion comprising, by mass percentage:

[0035]

[0036] It is understood that polyether-modified twin-structure polysiloxane wetting agents include, but are not limited to, TEGO Twin4000, Rieter Chemical LD-8400, and RianPont2504; polyether-modified hydroxyl-containing polydimethylsiloxane wetting agents include, but are not limited to, BYK-377 and Kramar 8530H.

[0037] In some of these examples, the wetting agent in the silica dispersion is selected from at least one of TEGO Twin 4000 and BYK-377.

[0038] In some of these examples, the silane coupling agent in the silica dispersion is selected from at least one of epoxy silane coupling agents, amino silane coupling agents, vinyl silane coupling agents, acrylate-based silane coupling agents, and isocyanate-based silane coupling agents.

[0039] It is understood that epoxy silane coupling agents include, but are not limited to, Shin-Etsu KBE-403 and Dow Corning Z-6040; vinyl silane coupling agents include, but are not limited to, Shin-Etsu KBE-1003 and Dow Corning Z-6300; and amino silane coupling agents include, but are not limited to, Shin-Etsu KBM-602 and Dow Corning Z-6011.

[0040] In some of these examples, the silane coupling agent in the silica dispersion is selected from at least one of epoxy silane coupling agents and vinyl silane coupling agents.

[0041] In some of these examples, the silane coupling agent in the silica dispersion is selected from at least one of KBE-1003 and KBE-403.

[0042] In some of these examples, the dispersant in the silica dispersion is a high molecular weight polymer dispersant, selected from at least one of polyether dispersants, polyester dispersants, polyurethane dispersants, polyacrylate dispersants, polyamide dispersants, and polyphosphate dispersants.

[0043] It is understood that polyether dispersants include, but are not limited to, TEGO Dispers 655 and BASF Efka FA4620; polyacrylate dispersants include, but are not limited to, BYK DISPERBYK-2055 and BYK DISPERBYK-2070.

[0044] In some of these examples, the dispersant in the silica dispersion is selected from at least one of polyether dispersants and polyacrylate dispersants.

[0045] In some of these examples, the dispersant in the silica dispersion is selected from at least one of TEGO Dispers 655 and BYKDISPERBYK-2055.

[0046] In some of these examples, the solvent in the silica dispersion is selected from at least one of butanone, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, toluene, xylene, and N,N-dimethylformamide.

[0047] Optionally, the solvent is selected from at least one of butanone and cyclohexanone.

[0048] In some of these examples, the silica dispersion has a silica particle size of 0.5 μm to 25 μm.

[0049] It is understood that the particle size (D50) of silica includes, but is not limited to, 0.5μm, 0.9μm, 1μm, 2μm, 4μm, 5μm, 8μm, 10μm, 12μm, 15μm, 18μm, 20μm, 21μm, 22μm, 23μm, and 25μm.

[0050] Optionally, the particle size of silica is 0.9 μm to 5 μm.

[0051] It is understood that there are no particular restrictions on the form of silica, including but not limited to spherical silica powder and non-spherical silica powder.

[0052] One embodiment of this application provides a method for preparing a silica dispersion, including steps S10 to S30:

[0053] Step S10: Provide raw materials according to the composition of the silica dispersion described above.

[0054] Step S20: Mix the wetting agent, silane coupling agent, solvent and silica and then stir for the first time to obtain the first slurry; the stirring time for the first time is 20 min to 40 min.

[0055] It is understood that the first stirring time includes, but is not limited to, 20 min, 22 min, 25 min, 28 min, 30 min, 32 min, 35 min, 38 min, and 40 min.

[0056] Optionally, the first stirring time is 30 minutes.

[0057] In some examples, in step S20, after the wetting agent, silane coupling agent and solvent are stirred evenly, silica is added for the first stirring.

[0058] Optionally, silica can be added while stirring.

[0059] Step S30: Mix the first slurry and the dispersant and then stir for the second time to obtain the second slurry; the sum of the first stirring time and the second stirring time is 65 min to 125 min.

[0060] In some of these examples, in step S30, the second stirring time is 30 min to 95 min.

[0061] It is understood that the second stirring time includes, but is not limited to, 30 min, 35 min, 40 min, 50 min, 60 min, 70 min, 80 min, and 90 min.

[0062] It is understandable that in step S30, after each second stirring period, solvent is added based on the amount of solvent evaporation to ensure that the amount of solvent in the final silica dispersion is within the aforementioned component ratio of the silica dispersion, thus ensuring that the solid content of the final silica dispersion is not too high. It is also understandable that the second stirring continues after adding solvent. Furthermore, it is understood that solvent can also be added in step S20.

[0063] In some of these examples, in step S30, the amount of solvent evaporation is checked and replenished every 20 to 30 minutes.

[0064] In some examples, in step S30, after adding the last amount of solvent to the formulation volume, the mixture is stirred for 2 to 10 minutes. Optionally, it is stirred for 5 minutes.

[0065] It is understandable that stirring is performed after the final addition of solvent to ensure that all components are mixed evenly with the solvent, while minimizing solvent evaporation.

[0066] Step S40: The second slurry is milled to obtain a silica dispersion; the milling time is 45 min to 180 min, and the feed flow rate is 0.8 L / min to 3 L / min.

[0067] It is understood that the grinding time includes, but is not limited to, 45 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min, and 180 min; and the feed flow rate of the grinding mill includes, but is not limited to, 0.8 L / min, 1 L / min, 1.2 L / min, 1.5 L / min, 2 L / min, 2.7 L / min, and 3 L / min.

[0068] In some of these examples, in step S40, the second slurry is sand-milled using a single-machine cyclic grinding process.

[0069] The preparation method of the above-mentioned silica dispersion is simple, the raw material components are readily available, and there are few restrictions on silica.

[0070] One embodiment of this application provides a resin composition comprising the above-described silica dispersion.

[0071] Adding the above-mentioned silica dispersion to the resin composition results in a better dispersion effect, which can solve the problem of easy agglomeration of traditional silica in the resin system. It also has a high solid content and good storage stability.

[0072] It is understood that metals, dielectric materials, and composite materials may be added to the resin composition, but are not limited to those that are metals, dielectric materials, and composite materials.

[0073] One embodiment of this application provides the use of the above-described resin composition in the preparation of an integrated circuit substrate. Another embodiment of this application provides an integrated circuit substrate whose raw materials include the above-described resin composition.

[0074] The above-mentioned resin composition is used to prepare integrated circuit substrates, which can reduce the coefficient of thermal expansion of each material, thereby effectively preventing warping of the substrate. Specific Implementation

[0076] The following examples of silica dispersions, their preparation methods, resin compositions, and their applications are provided in this application. It should be understood that the silica dispersions, their preparation methods, resin compositions, and their applications in this application are not limited to the following examples.

[0077] The sources of raw materials used in each embodiment and comparative example are as follows:

[0078] Butanone: Baling Petrochemical, China Petrochemical Corporation;

[0079] Cyclohexanone: Sinopec Baling Petrochemical Co., Ltd.

[0080] Polyether-modified twin-structure polysiloxane: TEGO Twin 4000, Evonik Industries, Germany;

[0081] Polyether-modified hydroxyl-containing polydimethylsiloxane: BYK-377, BYK Chemie, Germany;

[0082] Vinylsilane coupling agent: KBE-1003, Shin-Etsu Chemical Co., Ltd., Japan;

[0083] Epoxy silane coupling agent: KBE-403, Shin-Etsu Chemical Co., Ltd., Japan;

[0084] Spherical silica: FB-3SDC, D50 = 3.1μm, D90 = 5.9μm, Denki Kagaku Kogyo Co., Ltd., Japan;

[0085] Fused silica: RC008, D50 = 4.8 μm, D90 = 7.2 μm, Lianyungang Ruichuang New Materials Technology Co., Ltd.

[0086] Polyether dispersant: TEGO Dispers 655, Evonik Industries, Germany;

[0087] Polyacrylate dispersant: BYK DISPERBYK-2055, BYK Chemicals, Germany;

[0088] Polyether-modified polysiloxane: TEGO Wet 240, Evonik Industries, Germany;

[0089] Non-silicone wetting agent: BYK-399, BYK Chemicals, Germany.

[0090] Example 1

[0091] Add 21.5 wt% methyl ethyl ketone, 0.5 wt% polyether-modified twin-structure polysiloxane wetting agent TEGOTwin 4000, and 1 wt% vinyl silane coupling agent KBE-1003 to a 1L container in sequence, and stir evenly in a disperser at 2000 rpm (the highest speed of an IKAEUROSTAR 20digital). While stirring, add 75 wt% spherical silica and continue stirring at 2000 rpm for 30 min. Check the solvent evaporation and replenish it to the formula amount. Then add 2 wt% polyether dispersant TEGODispers 655 and continue stirring at 2000 rpm for 30 min. Check the solvent evaporation and replenish it to the formula amount. Continue stirring at 2000 rpm for 30 min. Check the solvent evaporation and replenish it to the formula amount. Continue stirring at 2000 rpm for 5 min. The total stirring time is 95 min. After stirring, 1 kg of dispersion to be ground was obtained. The slurry was milled using a single-machine circulating milling process (Jingchi Experimental Nano Sand Mill RP0.5). The dispersion was continuously stirred at 2000 rpm in the circulating tank, the feed flow rate was controlled at 2 L / min, and the milling cycle time was 90 min to obtain a silica dispersion.

[0092] Example 2

[0093] It is basically the same as Example 1, except that the solvent in Example 2 is cyclohexanone.

[0094] Example 3

[0095] The example is basically the same as Example 1, except that the wetting agent in Example 3 is an equal mass of polyether-modified hydroxyl-containing polydimethylsiloxane wetting agent BYK-377.

[0096] Example 4

[0097] The example is basically the same as Example 1, except that the silane coupling agent in Example 4 is an equal mass of epoxy silane coupling agent KBE-403.

[0098] Example 5

[0099] The example is basically the same as Example 1, except that the silica in Example 5 is an equal amount of molten silica RC008.

[0100] Example 6

[0101] The process is essentially the same as in Example 1, except that, by mass percentage, the silica dispersion comprises: 0.5 wt% of polyether-modified twin-structure polysiloxane wetting agent TEGO Twin 4000, 1 wt% of vinyl silane coupling agent KBE-1003, 50 wt% of spherical silica, 2 wt% of polyether dispersant TEGO Dispers 655, and 46.5 wt% of methyl ethyl ketone (MEK).

[0102] Example 7

[0103] The process is essentially the same as in Example 1, except that, by mass percentage, the silica dispersion comprises: 0.5 wt% of polyether-modified twin-structure polysiloxane wetting agent TEGO Twin 4000, 1 wt% of vinyl silane coupling agent KBE-1003, 80 wt% of spherical silica, 2 wt% of polyether dispersant TEGO Dispers 655, and 16.5 wt% of methyl ethyl ketone (MEK).

[0104] Example 8

[0105] The example is basically the same as Example 1, except that the dispersant in Example 8 is an equal mass of polyacrylate dispersant BYK DISPERBYK-2055.

[0106] Example 9

[0107] The process is essentially the same as in Example 1, except that 21.5 wt% methyl ethyl ketone (MEK), 0.5 wt% polyether-modified twin-structure polysiloxane wetting agent TEGO Twin 4000, and 1 wt% vinyl silane coupling agent KBE-1003 are added sequentially to a 1L container and stirred at 2000 rpm until homogeneous. While stirring, 75 wt% spherical silica is added and stirring is continued at 2000 rpm for 30 minutes. The solvent evaporation is checked and replenished to the required amount. Then, 2 wt% polyether dispersant TEGO Dispers 655 is added and stirring is continued at 2000 rpm for 30 minutes. The solvent evaporation is checked and replenished to the required amount. Stirring is continued at 2000 rpm for 5 minutes, for a total stirring time of 65 minutes. After stirring, the slurry is milled using a single-machine circulating milling process. The milling and dispersion are continuously carried out at 2000 rpm in the circulating tank, with the feed flow rate controlled at 2L / min and the milling circulation time at 90 minutes, to obtain a silica dispersion.

[0108] Example 10

[0109] It is basically the same as Example 1, except that the grinding cycle time is 45 minutes.

[0110] Example 11

[0111] It is basically the same as Example 1, except that the feed flow rate is controlled at 0.8L / min.

[0112] Comparative Example 1

[0113] The process is essentially the same as in Example 1, except that, by mass percentage, the silica dispersion comprises: 0.5 wt% of polyether-modified twin-structure polysiloxane wetting agent TEGO Twin 4000, 31 wt% of vinyl silane coupling agent KBE-100, 85 wt% of spherical silica, 2 wt% of polyether dispersant TEGO Dispers 655, and 11.5 wt% of methyl ethyl ketone (MEK).

[0114] Comparative Example 2

[0115] The process is essentially the same as in Example 1, except that, by mass percentage, the silica dispersion comprises: 0.1 wt% of polyether-modified twin-structure polysiloxane wetting agent TEGO Twin 4000, 1 wt% of vinyl silane coupling agent KBE-1003, 75 wt% of spherical silica, 2 wt% of polyether dispersant TEGO Dispers 655, and 21.9 wt% of methyl ethyl ketone (MEK).

[0116] Comparative Example 3

[0117] The method is basically the same as in Example 1, except that, by mass percentage, the silica dispersion comprises: 0.5 wt% of polyether-modified twin-structure polysiloxane wetting agent TEGO Twin 4000, 0.1 wt% of vinyl silane coupling agent KBE-1003, 75 wt% of spherical silica, 2 wt% of polyether dispersant TEGO Dispers655, and 22.4 wt% of methyl ethyl ketone (MEK).

[0118] Comparative Example 4

[0119] The method is basically the same as in Example 1, except that, by mass percentage, the silica dispersion comprises: 0.5 wt% of polyether-modified twin-structure polysiloxane wetting agent TEGO Twin 4000, 1 wt% of vinyl silane coupling agent KBE-1003, 75 wt% of spherical silica, 0.1 wt% of polyether dispersant TEGO Dispers 655, and 23.4 wt% of methyl ethyl ketone (MEK).

[0120] Comparative Example 5

[0121] Add 21.5 wt% methyl ethyl ketone (MEK), 0.5 wt% TEGOTwin 4000 (a polyether-modified twin-structure polysiloxane wetting agent), and 1 wt% KBE-1003 (a vinyl silane coupling agent) sequentially to a 1L container and stir until homogeneous. While stirring, add 75 wt% spherical silica and continue stirring at 2000 rpm for 30 minutes. Then add 2 wt% TEGO Dispers (a polyether dispersant) and continue stirring at 2000 rpm for 65 minutes, for a total stirring time of 95 minutes. After stirring, use a single-machine circulating milling process to grind the slurry. Continuous stirring and dispersion at 2000 rpm is maintained in the circulating tank, with a feed flow rate controlled at 2L / min and a milling circulation time of 90 minutes to obtain a silica dispersion. No solvent replenishment is required throughout the process.

[0122] The actual silica dispersion obtained by weight percentage includes: 0.5 wt% of polyether-modified twin-structure polysiloxane wetting agent TEGO Twin 4000, 1 wt% of vinyl silane coupling agent KBE-1003, 75 wt% of spherical silica, 2 wt% of polyether dispersant TEGO Dispers 655, and 10.9 wt% of methyl ethyl ketone (MEK).

[0123] Comparative Example 6

[0124] Add 21.5 wt% methyl ethyl ketone, 0.5 wt% polyether-modified twin-structure polysiloxane wetting agent TEGOTwin 4000, and 1 wt% vinyl silane coupling agent KBE-1003 to a 1L container in sequence and stir at 2000 rpm until homogeneous. While stirring, add 75 wt% spherical silica and continue stirring at 2000 rpm for 30 min. Then add 2 wt% polyether dispersant TEGODispers 655 and continue stirring at 2000 rpm for 10 min. Check the solvent evaporation and replenish to the formula amount. Continue stirring at 2000 rpm for 5 min, for a total stirring time of 45 min. After stirring, use a single-machine circulating grinding process to sand mill the slurry. Continuously stir and disperse at 2000 rpm in the circulating tank, control the feed flow rate at 2L / min, and the sand milling circulation time is 90 min to obtain a silica dispersion.

[0125] Comparative Example 7

[0126] Add 21.5 wt% methyl ethyl ketone (MEK), 0.5 wt% TEGOTwin 4000 (a polyether-modified twin-structure polysiloxane wetting agent), and 1 wt% KBE-1003 (a vinyl silane coupling agent) sequentially to a 1L container and stir at 2000 rpm until homogeneous. While stirring, add 75 wt% spherical silica and continue stirring at 2000 rpm for 30 minutes. Check the solvent evaporation and replenish to the required amount as per the formulation. Then add TEGO Dispers 655 (a polyether dispersant). Add 2wt% of the solvent and continue stirring at 2000 rpm for 30 min. Check the solvent evaporation and replenish it to the formula amount. Continue stirring at 2000 rpm for 30 min. Check the solvent evaporation and replenish it to the formula amount. Continue stirring at 2000 rpm for 5 min, for a total stirring time of 95 min. After stirring, use a single-machine circulating grinding process to sand mill the slurry. Continuously stir and disperse the slurry at 2000 rpm in the circulating tank. Control the feed flow rate at 2 L / min. The sand milling circulation time is 30 min to obtain a silica dispersion.

[0127] Comparative Example 8

[0128] It is basically the same as Example 1, except that the feed flow rate in Comparative Example 8 is controlled at 4L / min.

[0129] Comparative Example 9

[0130] The results are basically the same as in Example 1, except that the wetting agent in Comparative Example 9 is an equal mass of polyether-modified polysiloxane TEGO Wet 240, which has no twin structure.

[0131] Comparative Example 10

[0132] The example is basically the same as Example 1, except that the wetting agent in Comparative Example 10 is an equal mass of non-organosilicon wetting agent BYK-399.

[0133] The performance of the silica dispersions in each embodiment and comparative example was tested:

[0134] Solid content: Tested according to GB / T 2793-1995 standard, with the test temperature changed to 170℃ and the test time to 60min;

[0135] Stabilization period: Pour 50 mL of silica dispersion into a 50 mL glass graduated cylinder with a cap, and let it stand in the dark at 25 °C. Check the height of the supernatant every 7 days. The height of the supernatant is the sedimentation height of the dispersion. If the sedimentation is greater than 2 mL, the stabilization period is considered to be over. Record the stabilization period result as the number of days since the last check.

[0136] D90 before treatment: According to GB / T19077.1-2008 standard, the particle size distribution of the raw material without any treatment is tested and its D90 value is recorded;

[0137] D90 after treatment: The particle size distribution of the silica dispersion after treatment according to the methods of each embodiment and comparative example was tested and its D90 value was recorded in accordance with GB / T19077.1-2008 standard.

[0138] D90 after 30 days of standing: According to GB / T19077.1-2008 standard, for the silica dispersions processed by the methods of each embodiment and comparative example, the particle size distribution was tested after standing for 30 days and the D90 value was recorded; this test was not performed if the stabilization period was less than 30 days.

[0139] The test results of the embodiments are shown in Table 1.

[0140] Table 1

[0141]

[0142] The test results for the comparative model are shown in Table 2.

[0143] Table 2

[0144]

[0145] As shown in Tables 1 and 2, the silica dispersion provided in the examples has a solid content as high as 83.5%, exceeding the 280-day static stability period, and the particle size D90 fluctuation is less than 0.4 μm after 30 days of storage. In contrast, Comparative Example 1, with a larger silica content, only has a stability period of 84 days, and the particle size D90 increases significantly after 30 days, indicating that coarsening has already occurred after 30 days. Comparative Examples 2-4 adjusted the amount of wetting agent, silane coupling agent, or dispersant, and although the particle size D90 after treatment was similar to that of the examples, the stability period was less than or equal to 14 days, meaning it could not be stored stably for a long time. Comparative Example 5 did not involve solvent replenishment during preparation, resulting in an excessively high solid content, which shortened the stability period. The particle size D90 began to increase after 30 days of storage, which is not conducive to long-term storage. Comparative Example 6 shortened the stability period. The stirring time was too long, resulting in incomplete dispersion of silica and a shortened stabilization period. After 30 days, the particle size D90 began to increase significantly, which is not conducive to long-term storage. Comparative Example 7 shortened the grinding time during preparation, resulting in coarse silica particles suspended in the dispersion. After treatment, the particle size D90 hardly changed, and the stabilization period was also less than 30 days, making long-term stable storage impossible. Comparative Example 8 increased the feed flow rate during preparation, resulting in a shorter actual grinding time for silica, with results similar to Comparative Example 7. Comparative Examples 9 and 10 used other types of wetting agents that did not have the specific groups that define wetting agents. Although they could obtain a basically stable, high-solids-content, and easily dispersible silica dispersion, the stabilization period was less than 183 days, far less than the more than 280 days provided by the examples.

[0146] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0147] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A silica dispersion, characterized in that, By mass, it includes the following components: 50-80 parts of silica Wetting agent 0.4~1 part 0.5-1 part of silane coupling agent 1-2 parts of dispersant, and Solvent: 16-49 parts; The wetting agent is selected from at least one of polyether-modified twin-structure polysiloxane wetting agents and polyether-modified hydroxyl-containing polydimethylsiloxane wetting agents, specifically at least one of TEGO Twin 4000, LD-8400, RianPont2504, 8530H, and BYK-377. The mass ratio of the wetting agent to the silica is 1:(100~160). The silane coupling agent is selected from at least one of KBE-1003 and KBE-403. The dispersant is selected from at least one of TEGO Dispers 655 and BYKDISPERBYK-2055. The D50 particle size of the silica is 2 μm~5 μm. The solvent is selected from at least one of butanone, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, and N,N-dimethylformamide. The method for preparing the silica dispersion includes the following steps: Raw materials are provided according to the composition of the silica dispersion; The wetting agent, silane coupling agent, solvent and silica are mixed and stirred for the first time to obtain the first slurry; the first stirring time is 20 min to 40 min. The first slurry and the dispersant are mixed and then stirred a second time to obtain a second slurry; the sum of the first stirring time and the second stirring time is 65 min to 125 min. The second slurry is milled to obtain a silica dispersion; the milling time is 45 min to 180 min and the feed flow rate is 0.8 L / min to 3 L / min.

2. The silica dispersion as described in claim 1, characterized in that, The silica dispersion comprises the following components by mass parts: 50-80 parts of silica Wetting agent 0.5~1 part 0.8-1 part of silane coupling agent Dispersant 1.5-2 parts, and Solvent: 16-49 parts.

3. The silica dispersion as described in claim 1, characterized in that, The silica dispersion comprises the following components by mass parts: 50-80 parts of silica Wetting agent 0.5~0.8 parts, 0.9-1 part of silane coupling agent Dispersant 1.8~2 parts, and Solvent: 16-49 parts.

4. A method for preparing a silica dispersion, characterized in that, Includes the following steps: The raw materials are provided according to the components of the silica dispersion according to any one of claims 1 to 3; The wetting agent, silane coupling agent, solvent and silica are mixed and stirred for the first time to obtain the first slurry; the first stirring time is 20 min to 40 min. The first slurry and the dispersant are mixed and then stirred a second time to obtain a second slurry; the sum of the first stirring time and the second stirring time is 65 min to 125 min. The second slurry is milled to obtain a silica dispersion; the milling time is 45 min to 180 min and the feed flow rate is 0.8 L / min to 3 L / min.

5. A resin composition, characterized in that, Includes the silica dispersion as described in any one of claims 1 to 3.

6. The use of the resin composition as described in claim 5 in the preparation of integrated circuit substrates.

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