Diamond resin compound, resin composition, preparation method and application

Abstract

The diamond resin compound is prepared from the following raw materials: an inorganic filler 1, an inorganic filler 2, a coupling agent and epoxy resin I, the weight ratio of the inorganic filler 1 to the inorganic filler 2 to the coupling agent to the epoxy resin I is (1-40): (1-20): (1-5): (20-70); the inorganic filler 1 is diamond powder, and the D50 particle size of the diamond powder is 0.05-5 [mu] m. According to the method, the dispersity of diamond in epoxy resin can be remarkably improved, agglomeration is prevented, and the system compatibility is greatly improved. The diamond resin compound prepared in advance is added into the resin composition as a whole, so that the heat conductivity of the resin composition can be remarkably improved, and meanwhile, good flowability is kept. And the amino silane coupling agent is adopted, so that the compatibility of the diamond powder and an epoxy resin system is improved, the long-term stability of the system is remarkably improved, a stable interface layer is formed, interface separation between the filler and a matrix is reduced, and the layering phenomenon is effectively prevented.

Description

Technical Field

[0001] This invention relates to the field of polymer compound compositions, specifically to a diamond resin composite, resin composition, preparation method, and application. Background Technology

[0002] With the increasing intelligence and lightweighting of electronic devices, their packaging materials are also gradually moving towards miniaturization and high density. Highly integrated electronic devices generate a large amount of heat within a small space, requiring packaging materials with excellent thermal conductivity. Currently, a high proportion of spherical alumina or silicon micropowder is often used as filler material, but the thermal conductivity still needs improvement. Diamond powder has a high thermal conductivity, and its introduction can improve thermal conductivity; however, diamond powder has poor compatibility with epoxy resin, resulting in high contact and boundary thermal resistance, which affects the thermal conductivity of the composite material. Therefore, developing a composite material with good compatibility between diamond powder and epoxy resin to improve thermal conductivity is crucial.

[0003] Chinese invention patent CN112280252B discloses an epoxy composition and its application, which bonds and fixes the cutting head to the substrate. The toughness of the cured epoxy composition allows it to absorb vibrations from the substrate or the cutting head (hard metal material) during operation, thus achieving noise reduction. It also has good heat resistance, but its thermal conductivity still needs improvement. Chinese invention patent application CN120310490A discloses a high-performance electronic encapsulation adhesive based on graphene composite diamond micropowder and its preparation method. By adding surface-modified graphene composite diamond micropowder and fumed silica dispersant to the epoxy resin system, a highly efficient thermally conductive mesh is formed in the resin matrix, significantly improving thermal conductivity and compatibility. However, the large amount of thermally conductive filler added makes it difficult to apply and encapsulate microelectronic products. Summary of the Invention

[0004] To develop a composite material with good compatibility between diamond powder and epoxy resin, thereby improving thermal conductivity, the first aspect of the present invention provides a diamond resin composite material, the raw materials of which include inorganic filler 1, inorganic filler 2, coupling agent, and epoxy resin 1; the weight ratio of inorganic filler 1, inorganic filler 2, coupling agent, and epoxy resin 1 is (1-40):(1-20):(1-5):(20-70); the inorganic filler 1 is diamond powder, and the D50 particle size of the diamond powder is 0.05-5μm.

[0005] In one embodiment, the D50 particle size of the diamond powder is 50-1800 nm.

[0006] This invention incorporates diamond micro / nano powder and a coupling agent into epoxy resin 1. The inorganic filler 1, inorganic filler 2, coupling agent, and epoxy resin 1 are used in a weight ratio of (1-40):(1-20):(1-5):(20-70). One end of the coupling agent molecule reacts with the hydroxyl groups on the diamond surface, and the other end reacts with epoxy resin 1 to form a chemical bond. This effectively reduces the interfacial thermal resistance, allowing the high thermal conductivity of diamond to be fully utilized, significantly improving the dispersibility of diamond in epoxy resin 1, preventing agglomeration, and greatly enhancing the system compatibility.

[0007] In one embodiment, the coupling agent is an aminosilane coupling agent, which includes at least one of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, triamino-functionalized propyltrimethoxysilane, or N-cyclohexyl-γ-aminopropyltrimethoxysilane.

[0008] As one embodiment, the aminosilane coupling agent includes at least one of KH550, KH540, KH902, KH602, A-Link15, A-1524 CF, A-1120J or A-1170.

[0009] As one embodiment, the aminosilane coupling agent includes at least one of γ-aminopropyltriethoxysilane (KH550) or N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH540).

[0010] In one embodiment, the aminosilane coupling agent is γ-aminopropyltriethoxysilane.

[0011] In one embodiment, the inorganic filler 2 includes at least one of clay, mica powder, talc powder, bentonite, calcium carbonate, sodium sulfate, magnesium sulfate, calcium sulfate, alumina, aluminum nitride, silicon dioxide, zinc oxide, boron nitride, or diamond powder.

[0012] In one embodiment, the inorganic filler 2 includes at least one of silicon dioxide, aluminum nitride, or boron nitride.

[0013] In one embodiment, the inorganic filler 2 is silicon dioxide.

[0014] In one embodiment, the epoxy resin includes at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, polycyclic aromatic epoxy resin, or phenolic epoxy resin.

[0015] In one embodiment, the epoxy resin is a glycidyl ether epoxy resin.

[0016] In one embodiment, the epoxy resin is bisphenol F epoxy resin.

[0017] A second aspect of the present invention provides a method for preparing a diamond resin composite, comprising the following steps: Under an inert gas atmosphere, inorganic filler 1 and coupling agent are added to epoxy resin 1, stirred, and then sonicated. Then inorganic filler 2 is added, and sonication is continued to obtain diamond resin composite.

[0018] In one embodiment, the ultrasonic power is 150-2500W and the ultrasonic time is 5-30min.

[0019] In one embodiment, the power of the ultrasound is 1000-1500W, and the duration of the ultrasound is 5-15 minutes.

[0020] In one embodiment, the power of the ultrasound is 1000-1500W, and the duration of the ultrasound is 10 minutes.

[0021] In one embodiment, the inert gas is nitrogen.

[0022] This application employs ultrasonic treatment to provide high energy, which fully disperses diamond particles, allowing the diamond to first fully combine with epoxy resin to form a basic composite, and then combine with other fillers to form multiple composite structures of "diamond-epoxy resin-other fillers". This avoids the problem of uneven filler distribution caused by single ultrasonic treatment and further improves the compatibility of diamond in epoxy resin.

[0023] A third aspect of the present invention provides a resin composition comprising, by weight, 2-20 parts of the diamond resin composite described above, 5-30 parts of curing agent, 0.1-1 parts of coupling agent, 0.1-1 parts of colorant, 45-70 parts of solid filler, and 10-30 parts of epoxy resin.

[0024] In one embodiment, the solid filler includes at least one of clay, mica powder, talc powder, bentonite, calcium carbonate, sodium sulfate, magnesium sulfate, calcium sulfate, alumina, aluminum nitride, silicon dioxide, zinc oxide, boron nitride, and diamond powder.

[0025] In one embodiment, the solid filler includes at least one of silicon dioxide, aluminum nitride, or boron nitride.

[0026] In one embodiment, the solid filler is silicon dioxide.

[0027] In one embodiment, the D50 particle size of the solid filler is ≤5μm.

[0028] In one embodiment, the D50 particle size of the solid filler is 2 μm.

[0029] In one embodiment, the epoxy resin includes at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, polycyclic aromatic epoxy resin, or phenolic epoxy resin.

[0030] In one embodiment, the epoxy resin is bisphenol F epoxy resin.

[0031] In one embodiment, the curing agent includes at least one of amine curing agents, acid anhydride curing agents, or phenolic curing agents.

[0032] In one embodiment, the curing agent is 9,9-bis(4-aminophenyl)fluorene.

[0033] A fourth aspect of the present invention provides a method for preparing a resin composition, comprising the following steps: A diamond resin composite, curing agent, coupling agent, colorant, solid filler and epoxy resin are mixed and stirred evenly to obtain a resin composition.

[0034] A fifth aspect of the invention provides an application of a resin composition for sealing and filling protection of electronic devices.

[0035] Compared with the prior art, the present invention has the following beneficial effects: (1) The diamond resin composite, diamond powder, inorganic filler 2, coupling agent and epoxy resin 1 of the present invention adopt a weight ratio of (1-40): (1-20): (1-5): (20-70), which can significantly improve the dispersibility of diamond in epoxy resin 1, prevent agglomeration, and greatly improve the compatibility of the system.

[0036] (2) The diamond resin composite of the present invention adopts stepwise ultrasonic treatment to make diamond fully combine with epoxy resin to form a basic composite, and then combine with silicon dioxide. This avoids the problem of uneven filler distribution caused by single ultrasonic treatment. The preparation process is simple and efficient, with low time consumption, and forms a stable multi-component composite.

[0037] (3) The present invention applies the diamond resin composite to the resin composition. By adding the pre-prepared diamond resin composite as a whole to the resin composition, the thermal conductivity of the resin composition can be significantly improved while maintaining good fluidity.

[0038] (4) The present invention applies the diamond resin composite to the resin composition, and uses diamond powder of different particle sizes, silicon dioxide and solid fillers in combination to optimize the thermal network structure and improve the thermal conductivity.

[0039] (5) The diamond resin composite of the present invention uses an aminosilane coupling agent to improve the compatibility between diamond powder and epoxy resin system, significantly improve the long-term stability of the system, form a stable interface layer, reduce the interface separation between filler and matrix, and effectively prevent delamination. Attached Figure Description

[0040] Figure 1 A diagram of an apparatus for testing the flow time of resin compositions prepared for application examples and comparative examples.

[0041] In the diagram: 1. Silicon wafer; 2. Glass plate; 3. Gap between the chip and the glass plate; 4. Hot stage. Detailed Implementation

[0042] Example 1 A diamond resin composite is prepared from inorganic filler 1, inorganic filler 2, coupling agent, and epoxy resin 1; the weight ratio of inorganic filler 1, inorganic filler 2, coupling agent, and epoxy resin 1 is 15:5:1:29.

[0043] The inorganic filler 1 is diamond powder with a D50 particle size of 1800 nm, purchased from Bofeng Special Materials, with the grade DU1800.

[0044] The inorganic filler 2 is silicon dioxide with a D50 particle size of 50nm, purchased from Sanji Technology New Materials Co., Ltd., with the grade EQK0101.

[0045] The coupling agent is γ-aminopropyltriethoxysilane.

[0046] The epoxy resin is bisphenol F epoxy resin, purchased from Shengquan Group Co., Ltd., with the brand name SQE-8170.

[0047] A method for preparing a diamond resin composite includes the following steps: Under a nitrogen atmosphere, inorganic filler 1 and coupling agent were added to epoxy resin 1, stirred, and sonicated at 1500W for 10 min. Then inorganic filler 2 was added, and sonication was continued at 1000W for 10 min to obtain diamond resin composite.

[0048] Example 2 A diamond resin composite and its preparation method are described. The specific implementation method is the same as that in Example 1, except that the D50 particle size of the diamond powder is 50 nm, and it is purchased from Bofeng Special Materials with the grade DU50.

[0049] Example 3 A diamond resin composite and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that the coupling agent is N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.

[0050] Comparative Example 1 A diamond resin composite and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that the raw materials include inorganic filler 1, inorganic filler 2, and epoxy resin 1; the weight ratio of inorganic filler 1, inorganic filler 2, and epoxy resin 1 is 15:5:29.

[0051] Comparative Example 2 A diamond resin composite, with the same specific implementation as in Example 1, except that the preparation method of the diamond resin composite includes the following steps: Under a nitrogen atmosphere, inorganic filler 1 and coupling agent are added to epoxy resin 1, stirred, and then milled using a three-roll mill. Inorganic filler 2 is then added, and milling continues to obtain a diamond resin composite.

[0052] The three-roll mill has a 20μm inlet and a 10μm outlet gap, a rotation speed of 200rpm, and performs 5 milling cycles.

[0053] Application Example 1 A resin composition, the raw materials for which are prepared by weight include 16 parts of the diamond resin composite of Example 1, 11.5 parts of curing agent, 0.1 parts of coupling agent, 0.1 parts of color powder, 57.6 parts of solid filler, and 14.7 parts of epoxy resin.

[0054] The epoxy resin is bisphenol F epoxy resin, purchased from Shengquan Group Co., Ltd., with the brand name SQE-8170.

[0055] The curing agent is 9,9-bis(4-aminophenyl)fluorene.

[0056] The coupling agent is N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.

[0057] The pigment is carbon black.

[0058] The solid filler is silica with a D50 particle size of 2μm, purchased from Sanji Technology New Materials Co., Ltd., and its grade is EQH1603.

[0059] A method for preparing a resin composition includes the following steps: A diamond resin composite, curing agent, coupling agent, colorant, solid filler and epoxy resin are mixed and stirred evenly to obtain a resin composition.

[0060] Application Example 2 A resin composition and its preparation method are described. The specific implementation method is the same as that in Application Example 1, except that the diamond resin composite is prepared in Example 2.

[0061] Application Comparative Example 1 A resin composition, the raw materials for which are prepared include, by weight, 11.5 parts curing agent, 0.4 parts coupling agent, 0.1 parts color powder, 57.6 parts solid filler, 24 parts epoxy resin, 4.8 parts diamond powder, and 1.6 parts nano silica.

[0062] The diamond powder has a D50 particle size of 1.8 μm and was purchased from Bofeng Special Materials, with the grade DU1800.

[0063] The nano-silica has a D50 particle size of 50nm and was purchased from Sanji Technology New Materials Co., Ltd., with the grade EQK0101.

[0064] A method for preparing a resin composition includes the following steps: Epoxy resin, curing agent, coupling agent, colorant, solid filler, diamond powder and nano silica are mixed and stirred evenly to obtain a resin composition.

[0065] The remaining implementation methods are the same as in Application Example 1.

[0066] Application Comparative Example 2 A resin composition, the raw materials for which are prepared include, by weight, 11.5 parts curing agent, 0.4 parts coupling agent, 0.1 parts color powder, 59.73 parts solid filler, 24 parts epoxy resin, 3.2 parts diamond powder, and 1.07 parts nano silica.

[0067] The remaining implementation methods are the same as in Comparative Example 1.

[0068] Application Comparative Example 3 A resin composition, the raw materials for which are prepared include, by weight, 11.5 parts curing agent, 0.4 parts coupling agent, 0.1 parts color powder, 61.87 parts solid filler, 24 parts epoxy resin, 1.6 parts diamond powder, and 0.53 parts nano silica.

[0069] The remaining implementation methods are the same as in Comparative Example 1.

[0070] Performance testing 1. Viscosity: The viscosity of the diamond resin composites prepared in the examples and comparative examples was measured at 5 rpm at 25°C using a Brookfield DVNext viscometer. The test results are shown in Table 1.

[0071] 2. Static stability: The diamond resin composites prepared in the examples and comparative examples were placed at room temperature for 15 days, and the viscosity of the upper and lower layers was tested using a Brookfield DVNext viscometer. Viscosity change rate = viscosity after standing / viscosity before standing × 100%. The test results are shown in Table 1.

[0072] 3. Flow time test: such as Figure 1As shown in (a), silicon wafer 1 represents the chip, glass plate 2 represents the substrate, and 3 represents the 50μm gap between the chip and the glass plate. The length of glass plate 2 is 30mm, which is the flow distance. This structure is a test device. As shown in 1(b), the test device is placed on a 110℃ hot stage 4, and the prepared application examples and application comparison examples are respectively dispensed onto end A. Figure 1 (c) The flow time of the test resin composition to end B (flow distance of 30 mm) under gap 3 is shown in Table 3.

[0073] 3. Thermal conductivity: The resin compositions obtained in the application examples and comparative examples were placed in an oven at 165°C for 2 hours. The thermal conductivity of the cured materials was tested according to GB / T 22588-2008 standard. The test results are shown in Table 2.

[0074] Table 1

[0075] Table 2

Claims

1. A diamond resin composite, characterized in that, The raw materials for preparation include inorganic filler 1, inorganic filler 2, coupling agent, and epoxy resin 1; the weight ratio of inorganic filler 1, inorganic filler 2, coupling agent, and epoxy resin 1 is (1-40):(1-20):(1-5):(20-70); the inorganic filler 1 is diamond powder, and the D50 particle size of the diamond powder is 0.05-5μm.

2. The diamond resin composite according to claim 1, characterized in that, The coupling agent is an aminosilane coupling agent, which includes at least one of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, triamino-functionalized propyltrimethoxysilane, or N-cyclohexyl-γ-aminopropyltrimethoxysilane.

3. A method for preparing the diamond resin composite according to any one of claims 1-2, characterized in that, Includes the following steps: Under an inert gas atmosphere, inorganic filler 1 and coupling agent are added to epoxy resin 1, stirred, and then sonicated. Then inorganic filler 2 is added, and sonication is continued to obtain diamond resin composite.

4. The method for preparing the diamond resin composite according to claim 3, characterized in that, The ultrasonic power is 150-2500W, and the ultrasonic time is 5-30 minutes.

5. A resin composition, characterized in that, The raw materials for preparation include, by weight, 2-20 parts of the diamond resin composite as described in any one of claims 1-2, 5-30 parts of curing agent, 0.1-1 parts of coupling agent, 0.1-1 parts of colorant, 45-70 parts of solid filler and 10-30 parts of epoxy resin.

6. The resin composition according to claim 5, characterized in that, The solid filler includes at least one of clay, mica powder, talc powder, bentonite, calcium carbonate, sodium sulfate, magnesium sulfate, calcium sulfate, alumina, aluminum nitride, silicon dioxide, zinc oxide, boron nitride, or diamond powder.

7. The resin composition according to claim 5, characterized in that, The solid filler has a D50 particle size ≤ 5 μm.

8. The resin composition according to claim 5, characterized in that, Both epoxy resin one and epoxy resin two include at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, polycyclic aromatic epoxy resin, or phenolic epoxy resin.

9. A method for preparing a resin composition according to any one of claims 5-8, characterized in that, Includes the following steps: A diamond resin composite, curing agent, coupling agent, colorant, solid filler and epoxy resin are mixed and stirred evenly to obtain a resin composition.

10. An application of the resin composition according to any one of claims 5-8, characterized in that, It is used for sealing and filling protection of electronic devices.

Images