Compound amino silane coupling agent as well as preparation method and application thereof

Abstract

The invention provides a compound amino silane coupling agent and a preparation method and application thereof.The compound amino silane coupling agent is prepared from an amino silane coupling agent and an epoxy silane coupling agent.The compound amino silane coupling agent is prepared from the amino silane coupling agent and the epoxy silane coupling agent.The preparation method has the advantages that the compound amino silane coupling agent is prepared from the amino silane coupling agent and the epoxy silane coupling agent; the compound amino silane coupling agent can improve the adhesive property, heat resistance and chemical resistance of the material, and does not generate adverse effect on the stability of the material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of temporary bonding, and relates to a compounded amino silane coupling agent and a preparation method and application thereof, in particular to a compounded amino silane coupling agent for a temporary bonding adhesive material and a preparation method and application thereof. BACKGROUND

[0002] In the fields of semiconductor advanced packaging and precision device manufacturing, the performance of the temporary bonding adhesive material directly affects the process yield and device reliability. As a key functional component of the temporary bonding adhesive, the silane coupling agent needs to remain stable dispersion and structural stability in the adhesive system to ensure the sustainability of the interfacial bonding performance. However, when the existing amino silane coupling agent is used in the temporary bonding adhesive, the stability problem is prominent: on the one hand, the traditional coupling agent has insufficient compatibility with the adhesive matrix in terms of molecular structure, and is prone to aggregation and gelation during storage, which leads to the destruction of the uniformity of the adhesive and the decrease of the storage stability; on the other hand, the conventional coupling agent is prone to hydrolysis and group decomposition during the curing and high-temperature processing of the bonding adhesive due to insufficient structural weather resistance, which weakens its modification effect on the interface and ultimately affects the long-term stability of the bonding layer. With the development of semiconductor manufacturing towards ultra-precision, the temporary bonding adhesive needs to go through multiple complex processes, which puts higher requirements on the storage stability, processing stability and service environment stability of the silane coupling agent in the adhesive system.

[0003] The existing release layer materials for laser debonding on the market include epoxy systems, polyimide systems and polyamide acid systems, etc. A mature laser release material generally has good stability, and the shelf life of this type of material is usually required by chip packaging plants. However, since the materials that can be used for laser release layer usually have high activity, their stability is usually crucial during the material development process. In order to ensure that the release material after high-temperature curing has good adhesion on the surface of the silicon wafer and the glass carrier, an amino silane coupling agent is usually added to the adhesive, especially for epoxy and polyimide. Since the amino coupling agent has high activity, it is easy to cause gelation during storage, which affects the stability of the product, so it is necessary to develop a silane coupling agent that is suitable for such high-temperature curing materials and has good stability. SUMMARY

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a compound aminosilane coupling agent, its preparation method, and its application, particularly a compound aminosilane coupling agent for temporary bonding adhesive materials, its preparation method, and its application. The compound aminosilane coupling agent of the present invention reduces the reactivity of the amino coupling agent while ensuring good adhesion enhancement performance. The compound aminosilane coupling agent of the present invention is suitable for various temporary bonding resin materials that are reactive to amino groups. Adding this compound aminosilane coupling agent can improve the bonding performance, heat resistance, and chemical resistance of the material without adversely affecting its stability.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] On one hand, the present invention provides a compound aminosilane coupling agent, wherein the raw materials for preparing the compound aminosilane coupling agent include an aminosilane coupling agent and an epoxysilane coupling agent.

[0007] In this invention, aminosilane coupling agents and epoxysilane coupling agents are used to obtain compound aminosilane coupling agents, which are then added to temporary bonding materials to improve their adhesion, chemical resistance and heat resistance.

[0008] This invention addresses the problems of existing technologies by focusing on the innovative structural design of amino-based aminosilane coupling agents. Through molecular structure optimization and composite modification, it significantly improves the dispersion stability, chemical structural stability, and environmental tolerance stability of the coupling agent in temporary bonded adhesives. It not only solves the problems of easy gelation and storage failure of existing coupling agents in adhesive systems, but also ensures that they maintain stable interfacial modification functions under harsh conditions such as high and low temperature cycling and humid heat. This provides core support for achieving long-term and reliable bonding performance in temporary bonded adhesive materials, meeting the urgent needs of advanced manufacturing processes for the stability of bonding materials.

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

[0010] In a preferred embodiment, the epoxy silane coupling agent includes any one or a combination of at least two of γ-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, or 3-glycidoxypropyltriethoxysilane.

[0011] In a preferred embodiment, the mass ratio of the aminosilane coupling agent to the epoxysilane coupling agent is 1:(0.5-3), for example, 1:0.5, 1:0.8, 1:1, 1:1.5, 1:1.8, 1:2, 1:2.3, 1:2.5, 1:2.8 or 1:3, etc.

[0012] In this invention, the compound aminosilane coupling agent is prepared by reacting an aminosilane coupling agent and an epoxysilane coupling agent.

[0013] In a preferred embodiment, the reaction temperature is 60-150℃, for example 60℃, 65℃, 68℃, 70℃, 73℃, 75℃, 78℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃ or 150℃.

[0014] As a preferred embodiment, the reaction time is 0.5-3h, for example 0.5h, 0.8h, 1h, 1.5h, 1.8h, 2h, 2.5h, 2.8h or 3h.

[0015] On the other hand, the present invention provides a method for preparing the compounded aminosilane coupling agent as described above, the preparation method comprising the following steps:

[0016] The aminosilane coupling agent and the epoxysilane coupling agent are reacted to obtain the compound aminosilane coupling agent.

[0017] In a preferred embodiment, the reaction temperature is 60-150℃, for example 60℃, 65℃, 68℃, 70℃, 73℃, 75℃, 78℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃ or 150℃.

[0018] As a preferred embodiment, the reaction time is 0.5-3h, for example 0.5h, 0.8h, 1h, 1.5h, 1.8h, 2h, 2.5h, 2.8h or 3h.

[0019] On the other hand, the present invention provides a temporary bonding resin material comprising the compounded aminosilane coupling agent as described above.

[0020] In a preferred embodiment, the temporary bonding resin material comprises a resin solution and a compound aminosilane coupling agent as described above, wherein the amount of the compound aminosilane 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%.

[0021] On the other hand, the present invention provides the application of the compounded aminosilane coupling agent or temporary bonding resin material as described above in temporary bonding.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] This invention utilizes aminosilane coupling agents and epoxysilane coupling agents to obtain a compound aminosilane coupling agent. This compound aminosilane coupling agent can improve the bonding performance, heat resistance and chemical resistance of the material, without adversely affecting the stability of the material. Detailed Implementation

[0024] 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.

[0025] 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.

[0026] Example 1

[0027] 40 parts by weight of γ-aminopropyltriethoxysilane and 60 parts by weight of γ-glycidoxypropyltrimethoxysilane were mixed evenly at room temperature, and then heated to 100°C under a nitrogen atmosphere and reacted for 2 hours to obtain a compound aminosilane 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.

[0028] Example 2

[0029] 50 parts by weight of γ-aminopropyltriethoxysilane and 50 parts by weight of γ-glycidoxypropyltrimethoxysilane were mixed evenly at room temperature, and then heated to 100°C under a nitrogen atmosphere and reacted for 2 hours to obtain a compound aminosilane 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.

[0030] Example 3

[0031] 40 parts by weight of γ-aminopropylmethyldiethoxysilane and 60 parts by weight of 3-glycidyl etheroxypropylmethyldiethoxysilane were mixed evenly at room temperature, and then heated to 80°C under a nitrogen atmosphere and reacted for 1 hour to obtain a compound aminosilane 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.

[0032] Example 4

[0033] 40 parts by weight of γ-aminopropyltriethoxysilane and 20 parts by weight of γ-glycidyl etheroxypropyltriethoxysilane were mixed evenly at room temperature, and then heated to 150°C under a nitrogen atmosphere for 0.5 h to obtain a compound aminosilane coupling agent. This agent was added to a soluble polyimide solution to prepare a temporary release layer material, with the addition amount accounting for 30% of the resin mass. Then, its aging stability and adhesion to the substrate after high-temperature curing were tested.

[0034] Example 5

[0035] 40 parts by weight of γ-aminopropylmethyldiethoxysilane and 120 parts by weight of 3-glycidyl etheroxypropyltriethoxysilane were mixed evenly at room temperature, and then heated to 120°C under a nitrogen atmosphere and reacted for 1 hour to obtain a compound aminosilane coupling agent. This agent was added to a soluble polyimide solution to prepare a temporary release layer material, with the addition amount accounting for 20% of the resin mass. Then, its aging stability and adhesion to the substrate after high-temperature curing were tested.

[0036] Example 6

[0037] 40 parts by weight of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and 80 parts by weight of γ-glycidyl etheroxypropyltriethoxysilane were mixed evenly at room temperature, and then heated to 60°C under a nitrogen atmosphere and reacted for 3 hours to obtain a compound aminosilane coupling agent. This agent was added to a soluble polyimide solution to prepare a temporary release layer material, with the addition amount accounting for 5% of the resin mass. Then, its aging stability and adhesion to the substrate after high-temperature curing were tested.

[0038] Example 7

[0039] 40 parts by weight of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane and 40 parts by weight of γ-glycidoxypropyltrimethoxysilane were mixed evenly at room temperature, and then heated to 80°C under a nitrogen atmosphere and reacted for 2 hours to obtain a compound aminosilane coupling agent. This 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.

[0040] Example 8

[0041] 40 parts by weight of γ-aminopropylmethyldiethoxysilane and 90 parts by weight of 3-glycidyl etheroxypropylmethyldiethoxysilane were mixed evenly at room temperature, and then heated to 120°C under a nitrogen atmosphere and reacted for 2 hours to obtain a compound aminosilane coupling agent. This agent was added to a soluble polyimide solution to prepare a temporary release layer material, with the addition amount accounting for 45% of the resin mass. Then, its aging stability and adhesion to the substrate after high-temperature curing were tested.

[0042] Comparative Example 1

[0043] 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.

[0044] Comparative Example 2

[0045] A temporary release layer material was prepared by directly adding γ-glycidoxypropyltrimethoxysilane 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.

[0046] Comparative Example 3

[0047] 40 parts by weight of γ-aminopropyltriethoxysilane and 60 parts by weight of γ-glycidoxypropyltrimethoxysilane were mixed evenly at room temperature without heating and reaction, and then directly 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.

[0048] Performance testing:

[0049] (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.

[0050] (2) Adhesion 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 adhesion was tested using the cross-cut test. The test standard was GBT9286-1998 Scratch test of paint and varnish film.

[0051] Each embodiment and comparative example was tested according to the above method, and the results are shown in Table 1:

[0052] Table 1

[0053]

[0054] As can be seen from Application Example 1 and Comparative Example 1 in the table, although the epoxy silane coupling agent alone has no effect on the stability of the adhesive solution, it also fails to improve the adhesion of polyimide to the substrate. A comparison between Example 1 and Comparative Example 2 shows that the amino silane coupling agent alone has high activity, leading to rapid gelation and failure of the adhesive solution upon addition. A comparison between Example 1 and Comparative Example 3 indicates that the compounded coupling agent can significantly improve the adhesion of polyimide, but its stability remains poor. This is because the residual anhydride and terminal anhydride in the polyimide can react with the amino group to form chemical bonds, ensuring the bonding strength between them. However, due to the high reactivity of the primary amine, it easily forms crosslinking points in the polyimide solution. Furthermore, the hydrolysis of the siloxy groups generates a three-dimensional network structure, resulting in rapid gelation of the polyimide solution. The epoxy silane coupling agent, because it has no reactivity with the polyimide resin, cannot improve its adhesion and has no effect on its stability. When the two coupling agents are physically mixed, the primary amine and epoxy groups hardly react at room temperature, therefore the improvement in stability is not significant. Examples 1-8 show that the compound aminosilane coupling agent synthesized by heating reaction can significantly improve the adhesion of polyimide to the substrate, while having little impact on the stability of the polyimide solution, thus meeting the stability and adhesion requirements of similar temporary bonding materials.

[0055] The applicant declares that the present invention is illustrated by the above embodiments to demonstrate the compound aminosilane coupling agent, its preparation method, and its application. However, the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A compound aminosilane coupling agent, characterized in that, The raw materials for preparing the compound aminosilane coupling agent include aminosilane coupling agent and epoxysilane coupling agent.

2. The compounded aminosilane coupling agent according to claim 1, characterized in that, The aminosilane coupling agent is a bifunctional coupling agent containing a primary or secondary amine. 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.

3. The compounded aminosilane coupling agent according to claim 1 or 2, characterized in that, The epoxy silane coupling agent includes any one or a combination of at least two of γ-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropylmethyldiethoxysilane, γ-glycidyl etheroxypropyltriethoxysilane, or 3-glycidyl etheroxypropyltriethoxysilane.

4. The compounded aminosilane coupling agent according to any one of claims 1-3, characterized in that, The mass ratio of the aminosilane coupling agent to the epoxysilane coupling agent is 1:(0.5-3).

5. The compounded aminosilane coupling agent according to any one of claims 1-4, characterized in that, The compound aminosilane coupling agent is prepared by reacting an aminosilane coupling agent and an epoxysilane coupling agent. Preferably, the reaction temperature is 60-150℃ and the reaction time is 0.5-3h.

6. The method for preparing the compounded aminosilane coupling agent according to any one of claims 1-5, characterized in that, The preparation method includes the following steps: The aminosilane coupling agent and the epoxysilane coupling agent are reacted to obtain the compound aminosilane coupling agent.

7. The preparation method according to claim 6, characterized in that, The reaction temperature is 60-150℃, and the reaction time is 0.5-3h.

8. A temporary bonding resin material, characterized in that, The temporary bonding resin material includes any one of the compounded aminosilane coupling agents according to claims 1-5.

9. The temporary bonding resin material according to claim 8, characterized in that, The temporary bonding resin material comprises a resin solution and a compound aminosilane coupling agent according to any one of claims 1-5, wherein the amount of the compound aminosilane coupling agent added to the resin solution is 0.1-50% of the resin mass.

10. The use of the compounded aminosilane coupling agent according to any one of claims 1-5 or the temporary bonding resin material according to claim 8 or 9 in temporary bonding.

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