Temporary adhesive composition and temporary adhesive solution

Abstract

To provide a temporary adhesive composition and a temporary adhesive solution.SOLUTION: A temporary adhesive composition contains a main resin which is at least one selected from the group consisting of an epoxy resin, an alkyd resin, a phenol resin, a polyurethane resin and a polyester polyol resin, and a polyhydrocarbyl resin having a functional group whose at least one is reacted with the main resin and can form a polyurethane bond, wherein with respect to 100 wt.% of the temporary adhesive composition, the main resin is 20 wt.% to 35 wt.%, and the polyhydrocarbyl resin is 15 wt.% to 30 wt.%. A temporary adhesive layer formed from the same can have high rigidity.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a temporary adhesive composition and a temporary adhesive solution, and more particularly to a temporary adhesive composition and a temporary adhesive solution that form a highly rigid temporary adhesive layer. [Background technology]

[0002] In semiconductor processing, temporary bonding is a critical step in the later stages of wafer fabrication, used to bond fabricated wafers to carriers for subsequent operations such as thinning, testing, and packaging, after which the wafers are separated from the carrier.

[0003] However, conventional temporary adhesives can cause problems such as wafer warpage and grain slippage due to stress generated during thinning operations. Furthermore, conventional temporary adhesives are attached to the dielectric layer (e.g., polyimide) of the protective layer during processing operations, which can cause delamination of the substrate due to the dielectric layer absorbing moisture and generating gas.

[0004] In view of this, there is an urgent need to provide a temporary adhesive composition with high stiffness to solve the problems of grain sliding and substrate delamination. Summary of the Invention [Means for solving the problem]

[0005] One aspect of the present invention provides a temporary adhesive composition comprising a specific content of a main resin and a polyhydrocarbyl resin, wherein the resulting temporary adhesive forms a highly rigid temporary adhesive layer that can avoid the problems of grain sliding and delamination of substrates.

[0006] Another aspect of the present invention provides a temporary adhesive comprising the temporary adhesive composition of the above aspect.

[0007] According to one aspect of the present invention, there is provided a temporary adhesive composition comprising a main resin, which is at least one selected from the group consisting of an epoxy resin, an alkyd resin, a phenolic resin, a polyurethane resin, and a polyester polyol resin, and at least one polyhydrocarbyl resin having a functional group capable of reacting with the main resin to form a polyurethane bond, wherein the main resin is 20 wt% to 35 wt% and the polyhydrocarbyl resin is 15 wt% to 30 wt% relative to 100 wt% of the temporary adhesive composition.

[0008] According to an embodiment of the present invention, when the main resin is a polyester polyol resin, the molecular weight of the polyester polyol resin is 5,000-50,000.

[0009] According to one embodiment of the present invention, the temporary adhesive composition further comprises a solvent including at least one of N-methylpyrrolidone, butanone, a dibasic ester, and cyclohexanone.

[0010] According to one embodiment of the present invention, the polyhydrocarbyl resin comprises cyanate or isocyanate functional groups.

[0011] According to one embodiment of the present invention, the heat resistance temperature of the temporary adhesive composition is 350°C to 405°C.

[0012] According to one embodiment of the present invention, the complex viscosity of the temporary adhesive composition at 100°C to 160°C is less than 1000 Pa·s.

[0013] According to one embodiment of the present invention, after the temporary adhesive composition is heated at a temperature of 50°C to 300°C for 10 minutes or more, the temporary adhesive composition has a storage modulus of 5 MPa to 50.5 MPa at 200°C.

[0014] According to one embodiment of the present invention, the temporary adhesive composition is dissolved in an alkaline solution containing at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and monoethanolamine.

[0015] According to one embodiment of the present invention, the temporary adhesive composition has a cleaning rate of 2 μm / min to 7.5 μm / min with the alkaline solution at 60° C.

[0016] According to another aspect of the present invention, there is provided a temporary adhesive solution comprising the temporary adhesive composition. [Effects of the Invention]

[0017] Using the temporary adhesive composition and temporary adhesive solution of the present invention, with the specific contents of the main resin and polyhydrocarbyl resin, the resulting temporary adhesive forms a highly rigid temporary adhesive layer that can avoid the problems of grain sliding and delamination of the substrate, can be removed under alkaline conditions, and has high caulking properties. DETAILED DESCRIPTION OF THE INVENTION

[0018] The making and using of embodiments of the present invention are discussed in detail below. However, it will be understood that the embodiments provide many applicable inventive concepts that can be embodied in a variety of specific contexts. The specific embodiments discussed are for illustrative purposes only and are not intended to limit the scope of the invention.

[0019] As used herein, "around," "about," "approximately," or "substantially" generally means within 20%, 10%, or 5% of the stated numerical value or range.

[0020] "Rigidity" as described in the present invention refers to the ability of a film layer (eg, temporary adhesive layer) to withstand deformation, and is measured by storage modulus.

[0021] "Caulking ability" as described in this invention refers to the ability of the temporary adhesive to flow over the relief structures on the wafer during application, as determined using complex viscosity at process temperature.

[0022] As described above, the present invention provides a temporary adhesive composition and temporary adhesive solution with high caulking properties, which are obtained by using a specific content of main resin and polyhydrocarbyl resin to form a high-rigidity temporary adhesive layer that can avoid the problems of grain sliding and delamination of substrates and can be removed by washing with an alkaline solution.

[0023] The temporary adhesive composition of the present invention includes a main resin and a polyhydrocarbyl resin. In some embodiments, the main resin is about 20 wt% to about 35 wt%, the polyhydrocarbyl resin is about 15 wt% to about 30 wt%, and the remainder is a solvent, based on 100 wt% of the temporary adhesive composition. In some embodiments, the content of the main resin is at least 0.67 times the polyhydrocarbyl resin and up to 2.33 times the polyhydrocarbyl resin, and this mixing ratio can impart high rigidity to the temporary adhesive layer formed by the temporary adhesive composition.

[0024] If the content of the main resin is too low (e.g., less than 20 wt%), the complex viscosity of the temporary adhesive composition will be too high (e.g., above 1000 Pa·s), resulting in poor caulking properties. Conversely, if the content of the main resin is too high (e.g., above 35 wt%), the colloidal viscosity of the temporary adhesive composition will be too high (e.g., below 7000 cps), affecting the surface properties (e.g., flatness) of the temporary adhesive layer formed after coating. Furthermore, if the content of the polyhydrocarbyl resin is too low (e.g., less than 15 wt%), the temporary adhesive layer formed by the temporary adhesive composition will lack rigidity, making it prone to problems such as grain slippage and delamination during application. Furthermore, it will be unable to form a bond structure that is susceptible to alkaline solutions, making the temporary adhesive layer difficult to remove after application. Conversely, if the content of the polyhydrocarbyl resin is too high (e.g., above 30 wt%), the degree of cross-linking between materials will be increased, blocking the bond structure that is susceptible to alkaline solutions, affecting cleaning speed.

[0025] The primary resin is at least one selected from the group consisting of epoxy resin, alkyd resin, phenolic resin, polyurethane resin, and polyester polyol resin, preferably polyester polyol resin. In some embodiments, when the primary resin is polyester polyol resin, the molecular weight of the polyester polyol resin is 5,000 to 50,000, thereby providing an appropriate complex viscosity and imparting excellent caulking properties to the temporary adhesive composition. In some specific examples, the primary resin may be, for example, polyester polyol (company name: Aken Trading Co., Ltd., brand: SANNIX KC-229, molecular weight 5,000), polyester polyol (company name: Macroocean, brand: AL148, molecular weight 50,000), polyester-based polyurethane resin (company name: Anfeng Industrial Co., Ltd., brand: TPU-2091A), or polyester-based polyurethane resin (company name: Arakawa Chemical, brand: KL-540R).

[0026] While it is known to use a thermosetting resin or a block copolymer of acrylic ester and polystyrene to achieve increased rigidity, this known method reduces the rate of removal by subsequent alkaline cleaning solutions. Therefore, in some embodiments, at least one polyhydrocarbyl resin must contain a functional group capable of reacting with the hydroxyl groups (—OH groups) of the primary resin to form a polyurethane linkage, thereby making the temporary adhesive composition more easily removable by alkaline cleaning solutions (e.g., organic alkaline solutions) during subsequent cleaning operations. In the above embodiments, the functional group contained in the polyhydrocarbyl resin is a cyanate functional group or an isocyanate functional group. In some specific examples, the polyhydrocarbyl resin may be, for example, an aliphatic isocyanate (Company: Anfeng Industrial Co., Ltd., Brand: REXIN 1973 / 900, Molecular Weight 50,000) or a dicyclopentadiene cyanate resin (Company: Jin Guangsheng Materials Development Company, Brand: Vast-CE C03C, CAS No.: 135507-71-0).

[0027] In some embodiments, the solution may be at least one of N-methylpyrrolidone (NMP), butanone (methyl ethyl ketone; MEK), dibasic ester (DBE), and cyclohexanone (CYC), preferably a mixed solvent of a dibasic ester and another solvent. The dibasic ester has a property of multiple boiling points, which can prevent the temporary adhesive composition from bumping at high temperatures, and the temporary adhesive layer (e.g., temporary adhesive film) formed by the temporary adhesive composition has excellent film surface properties.

[0028] The heat resistance temperature of the temporary adhesive composition of the present invention is about 350°C to about 405°C, and preferably about 370°C to about 405°C. d (5%), which is the temperature at which the temporary adhesive composition is thermally decomposed until it loses 5% weight, and is evaluated using a thermogravimetric analyzer. Compared to conventional temporary adhesives, the temporary adhesive composition of the present invention has excellent heat resistance.

[0029] The complex viscosity of the temporary adhesive composition of the present invention at 100°C to 160°C is less than about 1000 Pa·s, preferably less than about 900 Pa·s, and more preferably less than about 500 Pa·s. In a typical die bonding process, the temporary adhesive composition is heated to a temperature of about 100°C to about 160°C. Therefore, if the temporary adhesive composition has a low complex viscosity at this temperature, it can have excellent caulking properties. Therefore, the temporary adhesive composition of the present invention has good caulking properties in the application process. Furthermore, the colloidal viscosity of the temporary adhesive composition of the present invention is about 2300 cps to about 7000 cps. The temporary adhesive layer formed after coating with the temporary adhesive composition having the above-mentioned specific colloidal viscosity has excellent film surface properties and excellent flatness.

[0030] After heating the temporary adhesive composition of the present invention at a temperature of 50°C to 300°C for 10 minutes or more, the storage modulus of this temporary adhesive composition at 200°C is about 5 MPa to about 50.5 MPa, preferably about 15 MPa to about 50.5 MPa, and more preferably about 20 MPa to about 50.5 MPa. The polyhydrocarbyl resin that does not react with the main resin in the temporary adhesive composition to form polyurethane bonds undergoes a self-crosslinking reaction at high temperatures to form a three-dimensional network structure, which improves the rigidity of the material and contributes to reducing the fluidity of the temporary adhesive composition at high temperatures. In order to prevent crystal grain slippage at high temperatures, the storage modulus must be at least 5 MPa. In other words, the temporary adhesive layer formed by the temporary adhesive composition of the present invention has high rigidity at high temperatures, which can reduce or avoid problems such as crystal grain slippage and delamination of substrates.

[0031] The temporary adhesive composition of the present invention can react to form polyurethane bonds, and is therefore soluble in alkaline solutions, allowing it to be removed using alkaline cleaning solutions after the process is complete. In some embodiments, the alkaline solution includes at least one organic alkaline solution, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and monoethanolamine. In some embodiments, the temporary adhesive composition has a cleaning rate of about 2 μm / min to about 7.5 μm / min at a temperature of about 60°C in an alkaline solution. This cleaning rate range can improve the efficiency of removing the adhesive layer formed by the subsequent temporary adhesive.

[0032] The present invention further provides a temporary adhesive solution that can be spin-coated onto a substrate to form a temporary adhesive layer (e.g., a temporary adhesive). The temporary adhesive solution includes the temporary adhesive composition described above. In some embodiments, the temporary adhesive solution is obtained by further diluting the temporary adhesive composition with a solvent, and the dilution ratio may be, for example, about 10% to about 60%. The same solvents as those described above can be used as the dilution solvent.

[0033] The application of the present invention is described below using several examples, but these are not intended to limit the present invention, and those skilled in the art of the present invention may make various changes and modifications without departing from the spirit and scope of the present invention. Example 1

[0034] The temporary adhesive composition of Example 1 contained 20 wt% polyester polyol resin (Macroocean, brand: AL148) as the main resin and 15 wt% polyhydrocarbyl resin with isocyanate functional groups (Anfeng Industrial Co., Ltd., brand: REXIN 1973 / 900) as the main resin, and used a mixture of dibasic ester and butanone as the solvent. Next, the complex viscosity, colloidal viscosity, washing speed, storage modulus, and heat resistance temperature of the temporary adhesive composition of Example 1 were measured, and the measurement results are shown in Table 1 below. Examples 2 to 8 and Comparative Examples 1 to 8

[0035] Examples 2 to 3 and Comparative Examples 1 to 7 are temporary adhesive compositions manufactured by the same method as Example 1, and detailed explanations are omitted here. The formulations and detection results are shown in Tables 1 and 2 below.

[0036] [Table 1]

[0037] [Table 2]

[0038] The heat resistance temperature test was performed using a thermogravimetric analyzer (TGA, brand: TA, model number: Q-500) by heating the temporary adhesive composition from room temperature 25°C to 500°C in a nitrogen gas (N2) atmosphere at a temperature increase rate of 20°C per minute. When the weight loss reaches 5%, the thermal decomposition temperature at this point is defined as the heat resistance temperature of the temporary adhesive composition. Cleaning Speed

[0039] First, the temporary adhesive composition was coated onto a substrate by spin coating, and then heated in an oven at 130°C for 20 minutes to remove the solvent. The composition was then heated in an anaerobic oven at 230°C for 6 hours, followed by another 2 hours at 260°C for complete aging, forming an adhesive layer on the substrate. The initial thickness of the adhesive layer was measured using a film thickness meter, and the substrate containing the adhesive layer was immersed in a cleaning solution, which was an organic solvent containing 2.38% tetramethylammonium hydroxide. The cleaning rate was defined as the time required for the adhesive layer on the substrate to be completely removed when the cleaning solution temperature was 60°C. Storage Modulus

[0040] The elastic properties of the sample were measured using a dynamic thermal analyzer (DMA, brand: TA, model number: Q800). The temporary adhesive composition was blade-coated onto a release film, placed in an anaerobic oven, heated at 230°C for 6 hours, and then heated at 260°C for 2 hours until fully aged, yielding a film-like sample. The aged sample was removed from the release film and its final thickness was measured. The sample was then analyzed by DMA. The measurement conditions were room temperature 25°C to 300°C, a heating rate of 10°C / min, and a stress (strain) of 0.1%. complex viscosity

[0041] The test was primarily conducted to determine the minimum complex viscosity of the sample (temporary adhesive composition) at temperatures between 100°C and 160°C. The test method involved blade-coating the temporary adhesive composition to form a film sample, then hot-pressing two identical film samples together (total thickness exceeding 500μm) at a temperature above the sample's softening temperature and below its crosslinking reaction temperature (160°C) to produce a measurement object. The measurement object was then analyzed using a rotational rheometer (Rheometer, brand: TA, model number: DHR-2). The test conditions were a room temperature of 25°C to 250°C, a heating rate of 10°C / min, and a pressure of 5N. Colloidal viscosity

[0042] The test was carried out using a rotational viscometer, and the temporary adhesive composition was kept at a constant temperature of 25°C ± 1°C using a thermostatic water bath. A rotor of model Z-91 was placed in the water bath and rotated to measure the colloidal viscosity of the temporary adhesive composition.

[0043] Based on Tables 1 and 2 above, when the polyhydrocarbyl resin content is less than 15 wt% (relative to 100 wt% of the temporary adhesive composition), the measured storage modulus of the temporary adhesive composition is low (less than 5 MPa); when the polyhydrocarbyl resin content exceeds 30 wt%, the temporary adhesive composition has a slow cleaning speed (less than 2 μm / min), i.e., it is difficult to remove with an alkaline solution; when the main resin content exceeds 35 wt% (relative to 100 wt% of the temporary adhesive composition), the colloidal viscosity of the temporary adhesive composition becomes too high, which affects the smoothness of the temporary adhesive layer formed after coating; and when the main resin content is less than 20 wt%, the complex viscosity of the temporary adhesive composition becomes too high, and the caulking properties become poor.

[0044] Based on the above examples, the temporary adhesive composition and temporary adhesive solution provided by the present invention have a specific content of main resin and polyhydrocarbyl resin, so that the temporary adhesive layer formed by the obtained temporary adhesive can avoid the problems of grain sliding and delamination of the substrate, and has high caulking ability at the application temperature, and can be quickly washed and removed with alkaline solution after processing.

[0045] Although the present invention has been disclosed in a number of embodiments as described above, these are not intended to limit the present invention, and since those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, the scope of protection of the present invention should be limited by the scope of the patent application to be attached later.

Claims

1. a primary resin, which is at least one selected from the group consisting of epoxy resins, alkyd resins, phenolic resins, polyurethane resins, and polyester polyol resins; at least one polyhydrocarbyl resin, at least one of which has functional groups capable of reacting with said primary resin to form polyurethane linkages; In a temporary adhesive composition comprising: A temporary adhesive composition, wherein the primary resin is 20 wt % to 35 wt % and the polyhydrocarbyl resin is 15 wt % to 30 wt % based on 100 wt % of the temporary adhesive composition.

2. 2. The temporary adhesive composition according to claim 1, wherein when the main resin is the polyester polyol resin, the molecular weight of the polyester polyol resin is 5,000 to 50,000.

3. 10. The temporary adhesive composition of claim 1, further comprising a solvent comprising at least one of N-methylpyrrolidone, butanone, a dibasic ester, and cyclohexanone.

4. 10. The temporary adhesive composition of claim 1, wherein the functional groups of the at least one polyhydrocarbyl resin comprise cyanate or isocyanate functional groups.

5. The temporary adhesive composition according to claim 1, wherein the temporary adhesive composition has a heat resistance temperature of 350°C to 405°C.

6. 2. The temporary adhesive composition according to claim 1, wherein the temporary adhesive composition has a complex viscosity of less than 1000 Pa·s at 100° C. to 160° C.

7. 2. The temporary adhesive composition according to claim 1, wherein after the temporary adhesive composition is heated at a temperature of 50°C to 300°C for 10 minutes or more, the temporary adhesive composition has a storage modulus at 200°C of 5 MPa to 50.5 MPa.

8. 2. The temporary adhesive composition according to claim 1, wherein the temporary adhesive composition is dissolved in an alkaline solution containing at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and monoethanolamine.

9. The temporary adhesive composition according to claim 8, wherein the temporary adhesive composition has a cleaning rate of 2 μm / min to 7.5 μm / min with the alkaline solution at 60° C.

10. A temporary adhesive solution comprising the temporary adhesive composition according to any one of claims 1 to 8.

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