An anti-settling thermal conductive laminated film and its preparation method and application

Abstract

The present invention provides an anti-settling thermally conductive laminated film and its preparation method and application. The anti-settling thermally conductive laminated film is composed of the following components by mass: 20-80 parts of a base epoxy resin, 10-50 parts of a heat-resistant epoxy resin, 1-50 parts of a curing agent, 0.1-3 parts of a curing accelerator, and 400-800 parts of modified alumina. The alumina powder is first surface-hydroxylated and then functionalized to react with a long-chain organic molecule solution, thereby introducing long-chain organic molecules on the surface of the alumina. This allows the modified alumina to be evenly dispersed in the epoxy resin system, is not easily sludged, and has good uniformity. At the same time, the interfacial thermal resistance between the epoxy resin system and the filler can be reduced, thereby improving the thermal conductivity and moisture-heat resistance of the laminated film. The anti-settling thermally conductive film prepared by the present invention has excellent fluidity, uniformity, moisture-heat resistance, and good thermal conductivity, and can be applied to IC substrate packaging.

Description

Technical Field

[0001] The present invention belongs to the field of IC packaging technology, and in particular relates to an anti-settling thermal conductive laminated film and a preparation method and application thereof. Background Art

[0002] With technological advancements, electronic devices will continue to develop towards high functionality and high integration. Heat-generating components generate even greater amounts of heat. If this heat cannot be dissipated quickly, it will significantly impact the operating speed and service life of electronic products. IC substrates packaged with traditional laminated films are no longer able to meet these requirements. The laminated film is in direct contact with the chip, which improves the thermal conductivity of the laminated film, facilitates heat transfer, and reduces the operating temperature of electronic devices. The current conventional method is to replace the filler with alumina, silicon nitride, silicon carbide, and other materials with higher thermal conductivity based on the original laminated film. Alumina is widely used due to its low price and availability. However, its thermal conductivity is relatively low compared to thermally conductive fillers such as silicon nitride, and a higher filler dosage is often required to achieve a higher thermal conductivity. When the alumina filling ratio is high, the sedimentation problem of alumina becomes more prominent, resulting in a narrower process window for the slurry and poorer uniformity of the thermally conductive laminated film, limiting its use.

[0003] Therefore, how to provide an anti-settling thermally conductive laminated film by modifying the filler material alumina and combining it with an epoxy resin system to improve the thermal conductivity, fluidity and uniformity of the laminated film so that it is suitable for the field of IC substrate packaging is a technical problem that technical personnel in this field urgently need to solve. Summary of the Invention

[0004] The object of the present invention is to provide an anti-settling thermal conductive laminated film and a preparation method and application thereof, so as to solve at least one of the above-mentioned technical problems.

[0005] To achieve the above objectives, the first aspect of the present invention provides an anti-settling thermally conductive laminated film, which is composed of the following components in parts by mass: 20-80 parts of a base epoxy resin, 10-50 parts of a heat-resistant epoxy resin, 1-50 parts of a curing agent, 0.1-3 parts of a curing accelerator, and 400-800 parts of modified alumina; the base epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, and alicyclic epoxy resin, and the mass fraction of the bisphenol A epoxy resin is 40-45 parts; the heat-resistant epoxy resin includes at least one of dicyclopentadiene phenol epoxy resin, biphenyl epoxy resin, naphthol epoxy resin, and multifunctional epoxy resin.

[0006] In the first aspect, the mass fraction of the matrix epoxy resin is 40-80 parts, the mass fraction of the heat-resistant epoxy resin is 15-45 parts, the mass fraction of the curing agent is 5-45 parts, the mass fraction of the curing accelerator is 1 part, and the mass fraction of the modified alumina is 500-600 parts.

[0007] In the first aspect, the curing agent includes at least one of dicyandiamide and phenolic resin.

[0008] In the first aspect, the curing accelerator includes an imidazole accelerator.

[0009] In the first aspect, the preparation method of the modified alumina includes the following steps: S1, adding a mixed solution of hydrogen peroxide and water in a mass ratio of 1:1 to alumina powder, stirring and reacting at 60-90°C, filtering, drying, and crushing to obtain surface hydroxylated alumina; S2, adding anhydrous ethanol to the surface hydroxylated alumina, stirring and reacting at 70°C for 4 hours, slowly adding a silane coupling agent solution dropwise, reacting at room temperature for 2 hours, filtering, washing, drying, and crushing to obtain functionalized alumina; S3, preparing a long-chain organic molecule solution; S4, adding the functionalized alumina to the long-chain organic molecule solution, stirring and reacting at 80-130°C for 1-4 hours, filtering, drying, and crushing to obtain modified alumina.

[0010] In the first aspect, in step S2, the silane coupling agent solution is prepared by adding a silane coupling agent to a mixed solution of pure water and anhydrous ethanol in a mass ratio of 2:1, mixing evenly, adjusting the pH value to 4.0 with acetic acid, and ultrasonically dispersing for 10 minutes to obtain a silane coupling agent solution.

[0011] In the first aspect, in step S3, the preparation of the long-chain organic molecule solution specifically includes the following steps: adding a bifunctional epoxy resin and an aromatic amine epoxy curing agent to propylene glycol methyl ether acetate in sequence, and stirring the reaction at 80-130°C until the solution becomes clear to obtain a long-chain organic molecule solution.

[0012] In the first aspect, when the silane coupling agent is an epoxy-containing coupling agent and the functionalized alumina in step S2 is surface epoxy-containing alumina, the long-chain organic molecule solution in step S3 is a double-terminated amino long-chain organic molecule solution I, wherein the mass ratio of the bifunctional epoxy resin and the aromatic amine epoxy curing agent is 1:2 or 2:3 or 3:4 or 4:5; when the silane coupling agent is a primary amino-containing coupling agent and the functionalized alumina in step S2 is surface primary amino-containing alumina; the long-chain organic molecule solution in step S3 is a double-terminated epoxy long-chain organic molecule solution II, wherein the mass ratio of the bifunctional epoxy resin and the aromatic amine epoxy curing agent is 2:1 or 3:2 or 4:3 or 5:4.

[0013] The second aspect of the present invention provides a method for preparing an anti-settling thermally conductive laminated film, which comprises: weighing 20-80 parts of a base epoxy resin, 10-50 parts of a heat-resistant epoxy resin, and 400-800 parts of modified alumina according to the mass fractions of the components of the anti-settling thermally conductive laminated film described in the first aspect into a planetary mixer, adding a solvent, stirring at 100-130°C for 0.5-3 hours, mixing evenly, and cooling to room temperature to obtain a first slurry; adding 1-50 parts of a curing agent and 0.1-3 parts of a curing accelerator to the first slurry, stirring at room temperature for 20-60 minutes to obtain a uniformly mixed second slurry; evenly coating the second slurry on a PET base film, placing it in an oven to dry to remove the solvent, removing the PET base film, and obtaining an anti-settling thermally conductive laminated film with a thickness of 10-500 μm.

[0014] A third aspect of the present invention provides a use of the anti-settling thermally conductive laminated film described in the first aspect in IC substrate packaging.

[0015] Beneficial effects:

[0016] The present invention provides an anti-settling thermally conductive laminated film, which is composed of the following components in parts by mass: 20-80 parts of a base epoxy resin, 10-50 parts of a heat-resistant epoxy resin, 1-50 parts of a curing agent, 0.1-3 parts of a curing accelerator, and 400-800 parts of modified alumina; the base epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, and alicyclic epoxy resin, and the bisphenol A epoxy resin has a mass fraction of 40-45 parts. This is used as the base material, and is combined with the heat-resistant epoxy resin to provide basic properties for the laminated film. The modified alumina is used as the filling material, so that the modified alumina can be uniformly dispersed in the epoxy resin system, is not easy to settle, has good fluidity and uniformity, and improves the thermal conductivity and moisture-heat resistance of the laminated film. At the same time, the curing agent and the curing accelerator are combined to increase the storage validity period of the laminated film, so that it meets the IC substrate packaging requirements. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the embodiments of this specification or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0018] Figure 1 Flowchart of the preparation method of modified alumina in an embodiment of the present invention. DETAILED DESCRIPTION

[0019] The present invention will be described in detail below in conjunction with specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly presented. It should be understood by those skilled in the art that these specific embodiments and examples are for illustrating the present invention, rather than for limiting the present invention.

[0020] Throughout this specification, unless otherwise specified, the terms used herein should be understood as having the same meaning as commonly used in the art. Therefore, 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 invention belongs. In the event of any conflict, the present specification shall take precedence.

[0021] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or obtained through existing methods.

[0022] The present application provides an anti-settling thermally conductive laminated film, which is composed of the following components in parts by mass: 20-80 parts of a base epoxy resin, 10-50 parts of a heat-resistant epoxy resin, 1-50 parts of a curing agent, 0.1-3 parts of a curing accelerator, and 400-800 parts of modified alumina; the base epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, and alicyclic epoxy resin, and the mass fraction of the bisphenol A epoxy resin is 40-45 parts; the heat-resistant epoxy resin includes at least one of dicyclopentadiene phenol epoxy resin, biphenyl epoxy resin, naphthol epoxy resin, and multifunctional epoxy resin.

[0023] Specifically, the present invention provides an anti-settling thermally conductive laminated film, which is composed of the following components in parts by mass: 20-80 parts of a base epoxy resin, 10-50 parts of a heat-resistant epoxy resin, 1-50 parts of a curing agent, 0.1-3 parts of a curing accelerator, and 400-800 parts of modified alumina; the base epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, and alicyclic epoxy resin, and the mass fraction of bisphenol A epoxy resin is 40-45 parts. This is used as the base material, and is combined with the heat-resistant epoxy resin to provide basic properties for the laminated film. The modified alumina is used as a filler material, so that the modified alumina can be evenly dispersed in the epoxy resin system, is not easy to settle, has good fluidity and uniformity, and improves the thermal conductivity and moisture-heat resistance of the laminated film. At the same time, the curing agent and curing accelerator are combined to increase the storage validity period of the laminated film, so that it meets the requirements of IC substrate packaging.

[0024] In some possible embodiments, the mass fraction of the base epoxy resin is 40-80 parts, the mass fraction of the heat-resistant epoxy resin is 15-45 parts, the mass fraction of the curing agent is 5-45 parts, the mass fraction of the curing accelerator is 1 part, and the mass fraction of the modified alumina is 500-600 parts.

[0025] Furthermore, the matrix epoxy resin may be selected from bisphenol A epoxy resin or bisphenol F epoxy resin with an epoxy equivalent of 170-300, or linear novolac epoxy resin with an epoxy equivalent of 120-150, or alicyclic epoxy resin with an epoxy equivalent of 100-300.

[0026] In some possible embodiments, the curing agent includes at least one of dicyandiamide and phenolic resin.

[0027] In the present application, the curing agent is a latent curing agent to increase the shelf life of the laminated film. As a preferred solution, the curing agent may include dicyandiamide or phenolic resin.

[0028] In some possible embodiments, the curing accelerator includes an imidazole accelerator.

[0029] In the present application, the selection of imidazole accelerators can adjust the storage time, curing temperature and curing speed of the laminated film.

[0030] In some possible embodiments, see Figure 1 , the preparation method of the modified alumina comprises the following steps:

[0031] S1. Add a mixed solution of hydrogen peroxide and water in a mass ratio of 1:1 to alumina powder, stir and react at 60-90° C., and obtain surface hydroxylated alumina by filtering, drying, and crushing.

[0032] S2. Add anhydrous ethanol to the surface hydroxylated alumina, stir and react at 70° C. for 4 hours, slowly dropwise add a silane coupling agent solution, react at room temperature for 2 hours, filter, wash, dry, and crush to obtain functionalized alumina;

[0033] S3, preparing a long-chain organic molecule solution;

[0034] S4. Add the functionalized alumina to the long-chain organic molecule solution, stir and react at 80-130° C. for 1-4 hours, filter, dry, and crush to obtain modified alumina.

[0035] By modifying conventional alumina powder, first surface hydroxylating the alumina powder and then functionalizing it to react with a solution of long-chain organic molecules, long-chain organic molecules are introduced onto the alumina surface. This allows the modified alumina to be evenly dispersed in the epoxy resin system, resisting sedimentation and exhibiting good uniformity. This also reduces the interfacial thermal resistance between the epoxy resin system and the filler, improving the thermal conductivity and moisture-heat resistance of the laminated film. In a specific embodiment, the conventional alumina powder can be spherical alumina with a diameter of 0.1-30 μm.

[0036] In some possible embodiments, in step S2, the silane coupling agent solution is prepared by adding a silane coupling agent to a mixed solution of pure water and anhydrous ethanol in a mass ratio of 2:1, mixing evenly, adjusting the pH value to 4.0 with acetic acid, and ultrasonically dispersing for 10 minutes to obtain a silane coupling agent solution.

[0037] In some possible embodiments, in step S3, the preparation of the long-chain organic molecule solution specifically includes the following steps: adding a bifunctional epoxy resin and an aromatic amine epoxy curing agent to propylene glycol methyl ether acetate in sequence, and stirring the reaction at 80-130° C. until the solution becomes clear, thereby obtaining a long-chain organic molecule solution.

[0038] In some possible embodiments, when the silane coupling agent is an epoxy-containing coupling agent, and the functionalized alumina in step S2 is surface epoxy-containing alumina, then the long-chain organic molecule solution in step S3 is a double-terminated amino long-chain organic molecule solution I, wherein the mass ratio of the bifunctional epoxy resin to the aromatic amine epoxy curing agent is 1:2 or 2:3 or 3:4 or 4:5; when the silane coupling agent is a primary amino-containing coupling agent, and the functionalized alumina in step S2 is surface primary amino-containing alumina; then the long-chain organic molecule solution in step S3 is a double-terminated epoxy long-chain organic molecule solution II, wherein the mass ratio of the bifunctional epoxy resin to the aromatic amine epoxy curing agent is 2:1 or 3:2 or 4:3 or 5:4.

[0039] Specifically, by adjusting the ratio of the bifunctional epoxy resin and the aromatic amine epoxy curing agent, the terminal groups of the long-chain organic molecules are epoxy or amino groups. The reactivity of the epoxy or primary amine groups on the surface of the functionalized alumina is then utilized to react with the long-chain organic molecules, thereby grafting the organic molecules onto the surface of the alumina, reducing the interfacial thermal resistance with the epoxy resin system and improving the thermal conductivity of the laminated film. The reaction formula of the bifunctional epoxy resin and the aromatic amine epoxy curing agent is shown below:

[0040] ;

[0041] Among them, A1 is or ,

[0042] A2 is or ,

[0043] A3 is , and n is an integer, , after testing, It is not conducive to heat transfer between the filling material alumina.

[0044] The bifunctional epoxy resin is preferably bisphenol A epoxy resin or bisphenol F epoxy resin; the aromatic amine curing agent is preferably 4,4'-diaminodiphenylmethane (DDM) or 4,4'-diaminodiphenyl ether (DDE); and the silane coupling agent is preferably γ-glycidyloxypropyltrimethoxysilane (KH560), γ-glycidyloxypropyltriethoxysilane (KH561), or γ-aminopropyltriethoxysilane (KH550).

[0045] Based on a general inventive concept, the present application also provides a method for preparing an anti-settling thermally conductive laminated film, the preparation method comprising:

[0046] (1) Weigh 20-80 parts of base epoxy resin, 10-50 parts of heat-resistant epoxy resin and 400-800 parts of modified alumina according to the weight proportions of the components of the anti-settling thermal conductive laminated film described in the first aspect in a planetary mixer, add a solvent, stir at 100-130° C. for 0.5-3 hours, mix well, and cool to room temperature to obtain a first slurry;

[0047] (2) adding 1-50 parts of a curing agent and 0.1-3 parts of a curing accelerator to the first slurry, stirring at room temperature for 20-60 minutes to obtain a uniformly mixed second slurry;

[0048] (3) The second slurry is evenly coated on a PET base film, and the film is placed in an oven for drying to remove the solvent, and the PET base film is removed to obtain an anti-settling thermal conductive laminated film with a thickness of 10-500 μm.

[0049] Specifically, after the second slurry is evenly coated on the PET base film, it is dried to remove the solvent. A layer of PET base film can be attached to the dried second slurry to form a laminated film product, which is easy to store and transport. When it needs to be used, the PET base film can be torn off.

[0050] Based on a general inventive concept, the present application also provides an application of the anti-settling thermally conductive laminated film described in the first aspect in IC substrate packaging.

[0051] The anti-settling thermally conductive laminated film provided in this application can be applied to IC carrier board packaging. The laminated film is adhered to the IC carrier board by hot pressing, so that the laminated film can be completely adhered to the chip and transfer the heat generated by the chip to the outside, thereby extending the service life of the chip.

[0052] The present application will be further described below in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present application only and are not intended to limit the scope of the present application. The experimental methods in the following examples where specific conditions are not specified are usually measured in accordance with national standards. If there are no corresponding national standards, then the methods are carried out in accordance with general international standards, conventional conditions, or according to the conditions recommended by the manufacturer.

[0053] The raw materials used in the embodiments and comparative examples are as follows:

[0054] Bisphenol A epoxy resin: CAS number: 25068-38-6; Manufacturer: Nan Ya 128;

[0055] Novolac epoxy resin: Nan Ya NPCN-703;

[0056] Dicyclopentadiene phenol epoxy resin: Changchun TaiLuck-TJ100;

[0057] Biphenyl type epoxy resin: tetramethyl biphenyl bisphenol A epoxy resin;

[0058] Naphthol epoxy resin: Brand: NC-7300L; Manufacturer: Nippon Kayaku;

[0059] Curing agent: dicyandiamide: CAS No.: 461-58-5, Xinxi Metallurgical Chemical;

[0060] Curing agent: phenolic resin: CAS No. 65733-76-8, Kolon KPH-F2004;

[0061] Curing accelerator: Imidazole curing accelerator, manufacturer: BASF 2E4MI, CAS number: 931-36-2, ingredient: 2-ethyl-4-methylimidazole;

[0062] Alumina powder: D50 particle size 2 μm; Manufacturer: DENKA Corporation DAW-01;

[0063] Aromatic amine epoxy curing agent curing agent: diaminodiphenylmethane: CAS number: 101-77-9; manufacturer: Shandong Xuchen Chemical.

[0064] The specific preparation steps of the modified alumina used in the examples and comparative examples are as follows:

[0065] (1) Surface hydroxylation of aluminum oxide: Add a mixed solution of 100 g of hydrogen peroxide and 100 g of pure water to 1000 g of aluminum oxide powder, stir and react at 60°C for 4 hours, filter, dry and crush to obtain surface hydroxylated aluminum oxide;

[0066] (2) Surface modification with silane coupling agent: 1000 g of surface hydroxylated alumina was added to anhydrous ethanol, stirred and reacted at 70°C for 4 hours, silane coupling agent solution was slowly added dropwise, reacted at room temperature for 2 hours, filtered, washed with anhydrous ethanol 5 times, dried, and crushed to obtain surface epoxy-modified alumina; wherein the preparation steps of the silane coupling agent solution include: adding 10 g of KH560 to a mixture of 20 g of pure water and 10 g of anhydrous ethanol, adjusting the pH value to 4.0 with acetic acid, ultrasonicating for 10 minutes, and letting it stand for 1 hour;

[0067] (3) Synthesis of long-chain organic molecules: Add bisphenol A epoxy resin and diaminodiphenylmethane in a mass ratio of 3:4 to propylene glycol methyl ether acetate solvent, and stir at 100°C until the solution is clear to obtain a double-terminated amino long-chain organic molecule solution I;

[0068] (4) Grafting on the surface of alumina: Add the surface epoxy-modified alumina obtained in (2) to the double-terminated amino long-chain organic molecule solution I in (3), and stir the reaction at 110°C for 2 hours to allow the end amino groups of the organic macromolecules to be capped with epoxy groups. The reaction solution is filtered, dried, and crushed to obtain modified alumina.

[0069] The raw material components in Examples 1-4 and Comparative Examples 1-6 of the present application are shown in Table 1 below in terms of mass fractions:

[0070] Table 1 Distribution ratio of each group of raw materials in Examples and Comparative Examples

[0071]

[0072] The performance of the anti-settling thermal conductive laminated films provided in Examples 1-4 and Comparative Examples 1-6 was tested. The specific testing process is as follows:

[0073] 1. Slurry stability: Turbiscan multiple light scattering instrument is used for testing. The slurry needs to be degassed before testing. The test time is 6 hours, the cycle is 5 minutes / time, and the light intensity fluctuation value at different time periods is taken. ;

[0074] 2. Glass transition temperature: DMA dual cantilever mode was used for testing, multi-strain method, and the heating rate was 5°C / min;

[0075] 3. Rheological viscosity: Use a rheometer for testing, with a heating rate of 5°C / min and the rheological viscosity value at 100°C;

[0076] 4. Thermal conductivity: Use hot wire method thermal conductivity meter to test, test voltage 1.5V, test 5 samples and take the average value;

[0077] 5. Copper bonding strength: The sample is made of two copper sheets overlapped and cured with a thermal conductive film, and the bonding strength of the sample is tested using the tensile mode of an electronic universal material testing machine;

[0078] 6. Bending strength: tested in three-point bending mode using an electronic universal material testing machine with a span of 36mm;

[0079] 7. Moisture and heat resistance evaluation: An uncured laminate film sample of 1 cm x 5 cm was bonded to a copper sheet and cured. The cured sample was then subjected to a high pressure cooking test (PCT). PCT conditions: 121°C, 100% relative humidity. The sample was ultrasonically scanned every 24 hours. If delamination between the laminate film and the copper sheet occurred, the corresponding test time was recorded. If no delamination occurred, the high pressure cooking test was continued until 192 hours had passed.

[0080] The test results are shown in Table 2 below:

[0081] Table 2 Test results

[0082]

[0083] It can be seen from the above table that in Examples 1-4 and Comparative Examples 3-6, the modified alumina prepared in this application is used as filler, and the light intensity fluctuation value is is low and increases with time. The value increases slightly, indicating that the modified alumina of the present application can be used as a filler to prevent the sedimentation of the filler, and the prepared slurry has good uniformity, which can extend the slurry coating time, facilitate operation, and further improve the uniformity of the laminated film after curing; when the experimental data of Example 1 and Comparative Example 3, and Example 3 and Comparative Example 5 are compared, it is shown that when the addition amount of modified alumina is less than 500 parts by mass, the thermal conductivity of the laminated film is less than 2W / m·k -1 , and the rheological viscosity and flexural strength of the laminated film are reduced, which does not meet the requirements; when the experimental data of Example 4 and Comparative Example 6 are compared, it is shown that when the addition amount of modified alumina is higher than 600 parts by mass, the thermal conductivity of the laminated film is higher than 2.36W / m·k -1 , resulting in excessive thermal conductivity and increased rheological viscosity, hindering slurry coating. Furthermore, in Comparative Examples 1-2, where modified alumina was not used, the laminated film produced easily delaminated from the copper sheet during autoclaving. This resulted in lower reliability during IC substrate packaging, increasing potential risks. This also demonstrates that laminated films produced using modified alumina exhibit excellent resistance to moisture and heat.

[0084] Finally, it should be noted that the terms "comprises," "includes," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements, but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0085] Although the preferred embodiments of the present invention have been described, those skilled in the art may make additional changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0086] Obviously, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if such changes and modifications fall within the scope of the claims and their equivalents, the present invention is intended to include such changes and modifications.

Claims

1. An anti-settling thermal conductive laminated film, characterized in that: The anti-settling thermal conductive laminated film is composed of the following components by mass: 40-80 parts of a base epoxy resin, 15-45 parts of a heat-resistant epoxy resin, 5-45 parts of a curing agent, 1 part of a curing accelerator, and 500-600 parts of modified alumina; the modified alumina is a long-chain organic molecule grafted with a functionalized alumina, the long-chain organic molecule is a double-terminated amino long-chain organic molecule or a double-terminated epoxy long-chain organic molecule, and the functionalized alumina is a surface epoxy aluminum oxide or a surface primary amino aluminum oxide; The matrix epoxy resin comprises at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin and alicyclic epoxy resin; The heat-resistant epoxy resin includes at least one of dicyclopentadiene phenol epoxy resin, biphenyl epoxy resin, naphthol epoxy resin and multifunctional epoxy resin; The preparation method of the modified alumina comprises the following steps: S1. Add a mixed solution of hydrogen peroxide and water in a mass ratio of 1:1 to alumina powder, stir and react at 60-90° C., and obtain surface hydroxylated alumina by filtering, drying, and crushing. S2. Add anhydrous ethanol to the surface hydroxylated alumina, stir and react at 70° C. for 4 hours, slowly dropwise add a silane coupling agent solution, react at room temperature for 2 hours, filter, wash, dry, and crush to obtain functionalized alumina; S3, preparing a long-chain organic molecule solution; S4, adding the functionalized alumina to the long-chain organic molecule solution, stirring and reacting at 80-130° C. for 1-4 hours, filtering, drying, and crushing to obtain modified alumina; In step S2, the silane coupling agent solution is prepared by adding a silane coupling agent to a mixed solution of pure water and anhydrous ethanol in a mass ratio of 2:1, mixing well, adjusting the pH value to 4.0 with acetic acid, and ultrasonically dispersing for 10 minutes to obtain a silane coupling agent solution; In step S3, the preparation of the long-chain organic molecule solution specifically includes the following steps: adding a bifunctional epoxy resin and an aromatic amine epoxy curing agent to propylene glycol methyl ether acetate in sequence, and stirring the mixture at 80-130° C. until the solution becomes clear, thereby obtaining a long-chain organic molecule solution; When the silane coupling agent is an epoxy-containing coupling agent, and the functionalized alumina in step S2 is surface epoxy-group alumina, the long-chain organic molecule solution in step S3 is a double-terminated amino long-chain organic molecule solution I, wherein the mass ratio of the bifunctional epoxy resin to the aromatic amine epoxy curing agent is 1:2 or 2:3 or 3:4 or 4:5; When the silane coupling agent is a primary amino-containing coupling agent, the functionalized alumina in step S2 is surface primary amino aluminum oxide; then the long-chain organic molecule solution in step S3 is a double-ended epoxy long-chain organic molecule solution II, wherein the mass ratio of the bifunctional epoxy resin to the aromatic amine epoxy curing agent is 2:1 or 3:2 or 4:3 or 5:

4.

2. The anti-settling thermally conductive laminated film according to claim 1, wherein: The matrix epoxy resin is bisphenol A epoxy resin or is compounded from bisphenol A epoxy resin and novolac epoxy resin.

3. The anti-settling thermally conductive laminated film according to claim 2, wherein: The curing agent includes at least one of dicyandiamide and phenolic resin.

4. The anti-settling thermally conductive laminated film according to claim 3, wherein: The curing accelerator includes an imidazole accelerator.

5. A method for preparing an anti-settling thermal conductive laminated film, characterized in that: The preparation method comprises: Weigh 40-80 parts by weight of the base epoxy resin, 15-45 parts by weight of the heat-resistant epoxy resin, and 500-600 parts by weight of the modified alumina according to the components of any one of claims 1-4 in a planetary mixer, add a solvent, stir at 100-130° C. for 0.5-3 hours, mix thoroughly, and cool to room temperature to obtain a first slurry; Add 5-45 parts of a curing agent and 1 part of a curing accelerator to the first slurry, and stir at room temperature for 20-60 minutes to obtain a uniformly mixed second slurry; The second slurry is evenly coated on a PET base film, and the film is placed in an oven for drying to remove the solvent, and the PET base film is removed to obtain an anti-settling thermal conductive laminated film with a thickness of 10-500 μm.

6. Use of the anti-settling thermally conductive laminated film according to any one of claims 1 to 4 in IC substrate packaging.

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