Amido silane coupling agent as well as preparation method and application thereof

Abstract

The invention provides an amido silane coupling agent and a preparation method and application thereof.The amido silane coupling agent is obtained through amidation reaction of an amino silane coupling agent and anhydride micromolecules, and the amido silane coupling agent can be flexibly added according to the formula requirement of a temporary bonding material; the amide group in the molecular structure can optimize the compatibility with a glue matrix, and the siloxane group can strengthen the interface bonding effect, so that the bonding performance of the temporary bonding material and the anti-agglomeration and anti-gel stability in the glue solution storage process are improved at the same time.

Description

Technical Field

[0001] This invention belongs to the field of temporary bonding materials, and relates to an amide-based silane coupling agent, its preparation method and application, and particularly to an amide-based silane coupling agent for temporary bonding adhesive materials, its preparation method and application. Background Technology

[0002] In cutting-edge fields such as advanced semiconductor packaging and precision device manufacturing, temporary bonding adhesives serve as core process auxiliary materials, and their comprehensive performance directly determines chip packaging yield, device operational reliability, and service life. Silane coupling agents, as key functional components of temporary bonding adhesives, bear the core mission of regulating the interfacial interaction of the adhesive system. They must simultaneously achieve two core objectives: first, maintaining a stable dispersion state during adhesive storage and application; and second, maintaining their structural integrity in complex process steps, thereby ensuring long-term stability of interfacial bonding performance.

[0003] However, the current mainstream aminosilane coupling agents, when applied to temporary bonding adhesives, suffer from a significant stability issue that has become a key bottleneck restricting technological upgrades. This manifests in two prominent problems: First, the molecular chain structure of traditional aminosilane coupling agents inherently lacks compatibility with temporary bonding adhesive matrices (such as epoxy and acrylate). Imbalances in intermolecular forces easily lead to particle agglomeration and localized gelation during storage, directly disrupting the homogeneity of the adhesive solution, significantly shortening the adhesive storage period, and increasing the risk of material loss during production. Second, the amino groups in the molecular structure of conventional coupling agents are too reactive. During bonding adhesive curing and high-temperature chip processing, they are susceptible to hydrolytic breakage and functional group decomposition reactions caused by moisture and high-temperature environments. This results in a significant reduction in their interface modification capabilities, ultimately causing problems such as decreased bonding layer peel strength and deterioration of damp heat resistance, seriously affecting device reliability.

[0004] As semiconductor manufacturing evolves towards ultra-precision technologies such as 3D stacking and Chiplet, temporary bonding adhesives need to undergo multiple stringent process tests, including high and low temperature cycling, damp heat aging, and chemical cleaning. This places far more stringent requirements on the storage stability, processing tolerance, and service stability of silane coupling agents than ever before, and existing products are no longer able to meet the technical requirements of advanced manufacturing processes. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide an amide-based silane coupling agent, its preparation method, and its applications. This invention precisely targets the stability limitations of existing aminosilane coupling agents, focusing on the molecular structural innovation of amide-based composite silane coupling agents. By introducing amide groups to optimize molecular polarity and spatial configuration, and combining composite modification techniques to regulate interfacial interactions, the invention achieves a synergistic improvement in the dispersion stability, chemical structural stability, and environmental tolerance stability of the coupling agent in temporary bonding adhesive systems. This invention not only fundamentally solves the industry pain points of traditional coupling agents such as easy gelation and storage failure, but also ensures that it continues to exert stable interfacial modification functions under extreme service conditions such as alternating high and low temperatures and humid heat, providing core technical support for temporary bonding adhesive materials to overcome the bottleneck of long-term reliable bonding performance, precisely matching the urgent needs for bonding material stability in fields such as advanced semiconductor packaging.

[0006] To achieve this objective, the present invention adopts the following technical solution: On one hand, the present invention provides an amide-based silane coupling agent, wherein the amide-based silane coupling agent is obtained by amidation reaction of an aminosilane coupling agent with a small molecule of an acid anhydride.

[0007] In this invention, the preparation of the amide-silane coupling agent is based on the core reaction pathway of "amino deactivation-amide generation". Through the amidation reaction of acid anhydride small molecules with aminosilane coupling agent, the active amino group (-NH2, -NH-) in the aminosilane molecule undergoes an addition ring-closing-ring-opening reaction with the acid anhydride group, and finally the chemical deactivation of the amino group is achieved and the amide group (-CONH-) is introduced simultaneously.

[0008] The amide-based silane coupling agent of the present invention can be flexibly added according to the formulation requirements of the temporary bonding material. The amide group in its molecular structure can optimize the compatibility with the adhesive matrix, and the siloxane group can strengthen the interfacial bonding effect, thereby simultaneously improving the adhesive performance of the temporary bonding material and the anti-agglomeration and anti-gelling stability of the adhesive solution during storage.

[0009] Preferably, the aminosilane coupling agent is a silane coupling agent containing a primary amine (-NH2) or a secondary amine (-NH-).

[0010] Preferably, the aminosilane coupling agent comprises any one or a combination of at least two of γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, or N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane.

[0011] Preferably, the acid anhydride small molecules include any one or a combination of at least two of acetic anhydride, phthalic anhydride, maleic anhydride, maleic anhydride, or pyromellitic dianhydride.

[0012] Preferably, the molar ratio of the aminosilane coupling agent to the acid anhydride small molecule is 1:(0.5-2), such as 1:0.5, 1:0.7, 1:0.9, 1:1.1, 1:1.3, 1:1.5, 1:1.7 or 1:2, etc.

[0013] Preferably, the temperature of the amidation reaction is 25-150℃ (e.g., 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, or 150℃, etc.), and the reaction time is 0.5-3h (e.g., 0.5h, 0.75h, 1h, 1.25h, 1.5h, 1.75h, 2h, 2.25h, 2.5h, or 3h, etc.).

[0014] On the other hand, the present invention provides a method for preparing the amide-based silane coupling agent as described above, the method comprising the following steps: The aminosilane coupling agent is obtained by amidation reaction with small acid anhydride molecules.

[0015] Preferably, the molar ratio of the aminosilane coupling agent to the acid anhydride small molecule is 1:(0.5-2), such as 1:0.5, 1:0.7, 1:0.9, 1:1.1, 1:1.3, 1:1.5, 1:1.7 or 1:2, etc.

[0016] Preferably, the temperature of the amidation reaction is 25-150℃ (e.g., 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, or 150℃, etc.), and the reaction time is 0.5-3h (e.g., 0.5h, 0.75h, 1h, 1.25h, 1.5h, 1.75h, 2h, 2.25h, 2.5h, or 3h, etc.).

[0017] On the other hand, the present invention provides a temporary bonding resin material comprising, as described above, an amide-silane coupling agent.

[0018] In a preferred embodiment, the temporary bonding resin material comprises a resin solution and an amide-silane coupling agent as described above, wherein the amount of the amide-silane coupling agent added to the resin solution is 0.1-50% of the resin mass, for example, 0.1%, 0.5%, 1%, 3%, 5%, 8%, 10%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%.

[0019] On the other hand, the present invention provides the application of the amide-based silane coupling agent or temporary bonding resin material as described above in temporary bonding.

[0020] Compared with the prior art, the present invention has the following beneficial effects: The amide-based silane coupling agent of the present invention can be flexibly added according to the formulation requirements of the temporary bonding material. The amide group in its molecular structure can optimize the compatibility with the adhesive matrix, and the siloxane group can strengthen the interfacial bonding effect, thereby simultaneously improving the adhesive performance of the temporary bonding material and the anti-agglomeration and anti-gelling stability of the adhesive solution during storage. Detailed Implementation

[0021] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0022] In this invention, unless otherwise specified, all equipment and raw materials are commercially available or commonly used in the industry. The methods described in the following embodiments are conventional methods in the art, unless otherwise specified.

[0023] In the embodiments of the present invention, the soluble polyimide solution used contains commercially available PI, brand name BASF matrix 5218, DMAC solvent, and has a solid content of 15%.

[0024] Example 1 0.1 mol of γ-aminopropyltriethoxysilane and 0.15 mol of acetic anhydride were mixed evenly at room temperature and then stirred under a nitrogen atmosphere for 1 hour to obtain an amide-silane coupling agent. This coupling agent was then added to a soluble polyimide solution to prepare a temporary release layer material. The amount added accounted for 15% of the resin mass. The aging stability and adhesion to the substrate after high-temperature curing were then tested.

[0025] Example 2 0.1 mol of γ-aminopropylmethyldiethoxysilane and 0.15 mol of phthalic anhydride were mixed evenly at room temperature, and then heated to 100°C and stirred for 2 hours under a nitrogen atmosphere to obtain an amide-based silane coupling agent. This agent was then added to a soluble polyimide solution to prepare a temporary release layer material, with the addition amount accounting for 15% of the resin mass. The aging stability and adhesion to the substrate after high-temperature curing were then tested.

[0026] Example 3 0.1 mol of γ-aminopropylmethyldiethoxysilane and 0.1 mol of maleic anhydride were mixed evenly at room temperature and then stirred under a nitrogen atmosphere for 0.5 h to obtain an amide-silane coupling agent. This coupling agent was then added to a soluble polyimide solution to prepare a temporary release layer material. The amount added accounted for 15% of the resin mass. The aging stability and adhesion to the substrate after high-temperature curing were then tested.

[0027] Example 4 0.1 mol of γ-aminopropyltriethoxysilane and 0.2 mol of maleic anhydride were mixed evenly at room temperature, and then stirred at 50°C for 3 hours under a nitrogen atmosphere to obtain an amide-based silane coupling agent. This coupling agent was added to a soluble polyimide solution to prepare a temporary release layer material. The amount added accounted for 10% of the resin mass. Then, its aging stability and adhesion to the substrate after high-temperature curing were tested.

[0028] Example 5 0.1 mol of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and 0.05 mol of pyromellitic dianhydride were mixed evenly at room temperature, and then stirred at 100°C for 0.5 h under a nitrogen atmosphere to obtain an amide-based silane coupling agent. This coupling agent was added to a soluble polyimide solution to prepare a temporary release layer material, with the addition amount accounting for 15% of the resin mass. Then, its aging stability and adhesion to the substrate after high-temperature curing were tested.

[0029] Example 6 0.1 mol of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane and 0.1 mol of phthalic anhydride were mixed evenly at room temperature, and then stirred at 80°C for 1 h under a nitrogen atmosphere to obtain an amide-based silane coupling agent. This coupling agent was then added to a soluble polyimide solution to prepare a temporary release layer material. The amount added accounted for 20% of the resin mass. The aging stability and adhesion to the substrate after high-temperature curing were then tested.

[0030] Comparative Example 1 A temporary release layer material was prepared by directly adding γ-aminopropyltriethoxysilane to a soluble polyimide solution, with the addition amount accounting for 15% of the resin mass. Then, its aging stability and adhesion to the substrate after high-temperature curing were tested.

[0031] Comparative Example 2 0.1 mol of γ-aminopropyltriethoxysilane and 0.02 mol of acetic anhydride were mixed evenly at room temperature and then stirred and reacted for 1 hour under a nitrogen atmosphere to obtain an amide-silane coupling agent. This coupling agent was then added to a soluble polyimide solution to prepare a temporary release layer material. The amount added accounted for 15% of the resin mass. The aging stability and adhesion to the substrate after high-temperature curing were then tested.

[0032] Comparative Example 3 0.1 mol of γ-aminopropyltriethoxysilane and 0.4 mol of acetic anhydride were mixed evenly at room temperature and then stirred and reacted for 1 hour under a nitrogen atmosphere to obtain an amide-silane coupling agent. This coupling agent was then added to a soluble polyimide solution to prepare a temporary release layer material. The amount added accounted for 15% of the resin mass. Then, its aging stability and adhesion to the substrate after high-temperature curing were tested.

[0033] Comparative Example 4 0.1 mol of γ-aminopropylmethyldiethoxysilane and 0.15 mol of phthalic anhydride were mixed evenly at room temperature, and then kept at 10°C and stirred for 2 hours under a nitrogen atmosphere to obtain an amide-based silane coupling agent. This agent was added to a soluble polyimide solution to prepare a temporary release layer material, with the addition amount accounting for 15% of the resin mass. Then, its aging stability and adhesion to the substrate after high-temperature curing were tested.

[0034] Comparative Example 5 0.1 mol of γ-aminopropylmethyldiethoxysilane and 0.15 mol of phthalic anhydride were mixed evenly at room temperature, and then heated to 100°C and stirred for 10 min under a nitrogen atmosphere to obtain an amide-based silane coupling agent. This agent was then added to a soluble polyimide solution to prepare a temporary release layer material, with the addition amount accounting for 15% of the resin mass. The aging stability and adhesion to the substrate after high-temperature curing were then tested.

[0035] Performance testing: (1) Aging stability: To quickly assess the effect of coupling agent on the stability of polyimide resin solution, accelerated aging tests were conducted on the examples and comparative examples. The test method was to place 100 ml of the example sample in an aging oven at 50°C for 7 days, and directly observe and record the gel time of each sample.

[0036] (2) Adhesive performance: The samples of the examples and comparative examples were spin-coated onto the surface of the silicon wafer and cured at 220°C to obtain a film layer with a thickness of 1μm. The adhesive strength was tested using the cross-cut test. The test standard was GBT9286-1998 Scratch test of paint and varnish film.

[0037] Each embodiment and comparative example was tested according to the above method, and the results are shown in Table 1: Table 1 As can be seen from Example 1 and Comparative Example 1 in the table, the unmodified aminosilane coupling agent has high activity, which can improve the adhesion of the adhesive film, but its aging stability is poor and it is difficult to store for a long time. The amide-based silane coupling agent obtained by deactivation with acetic anhydride, while retaining its coupling activity, significantly improves the stability of the adhesive solution. Examples 1, 5, 6 and Comparative Example 2 show that when the amount of acid anhydride participating in the reaction is too small, there is still a large amount of amino residue in the amide-based coupling agent product, resulting in poor adhesive solution stability. Examples 1, 4 and Comparative Example 3 show that when the amount of acid anhydride participating in the reaction is excessive, the silane coupling component in the product is too low, resulting in poor coupling activity and difficulty in improving the adhesion of the adhesive film. Examples 1 and Comparative Example 4 show that when the reaction temperature is too low, due to the poor activity of phthalic anhydride, the aminosilane coupling agent is not effectively deactivated, resulting in the product failing to effectively improve the stability of the adhesive solution. Examples 1 and Comparative Example 5 show that a reaction time that is too short will also lead to incomplete reaction, and the product cannot effectively improve the stability of the adhesive solution.

[0038] The applicant declares that this invention illustrates the amide-based silane coupling agent, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product, addition of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of this invention.

Claims

1. An amide-based silane coupling agent, characterized in that, The amide-based silane coupling agent is obtained by amidation reaction of an aminosilane coupling agent with small acid anhydride molecules.

2. The amide-based silane coupling agent according to claim 1, characterized in that, The aminosilane coupling agent is a silane coupling agent of a primary or secondary amine with an active hydrogen atom.

3. The amide-based silane coupling agent according to claim 1 or 2, characterized in that, The aminosilane coupling agent includes any one or a combination of at least two of γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, or N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane.

4. The amide-based silane coupling agent according to any one of claims 1-3, characterized in that, The acid anhydride small molecules include any one or a combination of at least two of acetic anhydride, phthalic anhydride, maleic anhydride, maleic anhydride, or pyromellitic dianhydride.

5. The amide-based silane coupling agent according to any one of claims 1-4, characterized in that, The molar ratio of the aminosilane coupling agent to the acid anhydride small molecule is 1:(0.5-2).

6. The amide-based silane coupling agent according to any one of claims 1-5, characterized in that, The amidation reaction is carried out at a temperature of 25-150°C for a duration of 0.5-3 hours.

7. The method for preparing the amide-based silane coupling agent according to any one of claims 1-6, characterized in that, The preparation method of the amide-silane coupling agent includes the following steps: The aminosilane coupling agent is obtained by amidation reaction with small acid anhydride molecules.

8. The preparation method according to claim 7, characterized in that, The molar ratio of the aminosilane coupling agent to the acid anhydride small molecule is 1:(0.5-2); Preferably, the temperature of the amidation reaction is 25-150°C, and the reaction time is 0.5-3 h.

9. A temporary bonding resin material, characterized in that, The temporary bonding resin material comprises the amide-based silane coupling agent according to any one of claims 1-6; Preferably, the temporary bonding resin material comprises a resin solution and an amide-silane coupling agent according to any one of claims 1-6, wherein the amount of the amide-silane coupling agent added to the resin solution is 0.1-50% of the resin mass.

10. The use of the amide-based silane coupling agent or temporary bonding resin material according to any one of claims 1-6 in temporary bonding.

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