Resin composition as well as preparation method and application thereof

Abstract

The invention provides a resin composition as well as a preparation method and application thereof. The resin composition comprises the following components in parts by weight: 50-120 parts of photosensitive resin and 10-40 parts of a thermal acid generator, the preparation raw materials of the photosensitive resin comprise a combination of epoxy resin and an amine curing agent. The components of the resin composition are designed, so that after the resin composition is cured on one surface of a substrate to form a film, the film surface is smooth and uniform, the adhesive ability to the substrate is good, the chemical resistance is good, and meanwhile, the resin composition has relatively high absorption on 532nm laser.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a resin composition, a preparation method thereof, and an application thereof. Background Art

[0002] With the rapid update of consumer electronics products, the development of 5G communication and high-end chips is also moving towards high frequency, high speed, multi-function and other directions. In order to meet the requirements of miniaturization and intelligence of integrated circuit chips, Moore's Law is challenged by physical limitations, which makes packaging technology particularly important in integrated circuit manufacturing. Advanced packaging technology focuses on three-dimensional stacking packaging, which can reduce the packaging volume, improve circuit performance, and reduce parasitic effects and time delay. Currently, a variety of three-dimensional packaging technologies have emerged, such as chip stacking packaging (PIP), package-on-package (POP), multi-chip packaging (MCP), system-in-package (SIP), wafer-level packaging (Wafer Level Package), and through-silicon via technology (TSV), etc.

[0003] Although different packaging forms are adopted, the control and thinning of the overall thickness are an inevitable trend, and the thickness requirements of stacked chips are becoming thinner. However, thinner silicon wafers also mean poorer structural strength. In order to ensure the stability of the silicon wafers during the processing, temporary bonding solutions are currently often used to achieve the holding control of the silicon wafers. According to different debonding methods, the temporary bonding process can be mainly divided into thermal slip, chemical, mechanical, and laser debonding methods. These methods have their own advantages and disadvantages. The thermal slip debonding method has low equipment cost, but it needs to reach a high temperature of 200 °C, and many flexible wearable materials and imaging devices cannot withstand it. The chemical debonding method also has low cost, and the ultra-thin device separation is achieved by dissolving the bonding glue with a solvent. However, the solvent exchange effect is poor, and the debonding process takes 8 to 24 hours, which is not suitable for large-scale production in the semiconductor industry. The mechanical debonding method uses special jigs to separate ultra-thin devices at room temperature, but due to the thin and brittle silicon wafers, they are easy to break, which has limitations. The infrared laser debonding method separates the devices by instantaneously degrading the polymer resin at high temperature to achieve stress-free separation between the silicon wafer and the support substrate, but the high temperature may damage the silicon devices, which has risks.

[0004] Currently, the existing release layer materials for 532 nm laser debonding on the market mostly add a large amount of light-absorbing fillers to achieve a low light transmittance. However, the addition of a large amount of fillers will not only cause the surface roughness of the release layer film to be too high and the bonding force with the glass to be insufficient, but also cause problems that are not easy to clean after debonding. Therefore, it is necessary to develop a resin composition without fillers, and the release layer formed by it has a high absorption of 532 nm laser. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a resin composition, a preparation method and an application thereof. By designing the components of the resin composition, after curing and forming a film on one surface of a substrate, the film surface is smooth and uniform, the bonding ability to the substrate is good, the chemical resistance is good, and at the same time, it has a high absorption of 532 nm laser.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] In the first aspect, the present invention provides a resin composition, which comprises the following components in parts by weight: 50-120 parts by weight of a photosensitive resin and 10-40 parts by weight of a thermal acid generator; the preparation raw materials of the photosensitive resin include a combination of an epoxy resin and an amine curing agent.

[0008] By designing the components of the resin composition, the present invention can be used as the preparation raw material for a release layer, for the temporary bonding of a silicon wafer, and the formed release layer has a high absorption of 532 nm laser, good bonding ability to a glass substrate, and good chemical resistance. Among them, the thermal acid generator can cause partial carbonization of the photosensitive resin during the curing process, thereby improving the light absorption coefficient of the release layer; the photosensitive resin can absorb most of the energy and decompose during the laser debonding process, thereby protecting the chip structure from laser ablation and realizing stress-free separation between the chip and the glass substrate.

[0009] In the present invention, the term "photosensitive resin" means that the resin is sensitive to laser and can be debonded by laser after curing.

[0010] The photosensitive resin in the resin composition is 50-120 parts by weight, for example, it can be 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, 100 parts by weight, 105 parts by weight, 110 parts by weight, 115 parts by weight, 120 parts by weight, etc.

[0011] The thermal acid generator in the resin composition is 10-40 parts by weight, for example, it can be 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, etc.

[0012] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the purpose and beneficial effects of the present invention can be better achieved and realized.

[0013] As a preferred technical solution, the epoxy resin includes an aliphatic epoxy resin and / or an aromatic epoxy resin.

[0014] Preferably, the epoxy resin includes any one or a combination of at least two of bisphenol A epoxy resin, bisphenol F epoxy resin, poly(1,4-butanediol diglycidyl ether), poly(propylene glycol diglycidyl ether), or poly(ethylene glycol diglycidyl ether).

[0015] Preferably, the epoxy equivalent of the epoxy resin is 150 - 350 g / mol, and for example, it can be 160 g / mol, 170 g / mol, 180 g / mol, 190 g / mol, 200 g / mol, 210 g / mol, 220 g / mol, 230 g / mol, 240 g / mol, 250 g / mol, 260 g / mol, 270 g / mol, 280 g / mol, 290 g / mol, 300 g / mol, 310 g / mol, 320 g / mol, 330 g / mol, 340 g / mol, etc.

[0016] Preferably, the amine curing agent includes any one or a combination of at least two of aminoazobenzene, 4-aminobiphenyl, 4-amino-2,3-dimethylazobenzene, aniline, toluidine, m-aminophenol, p-aminophenol, ethylenediamine, hexamethylenediamine, diethylenetriamine, or triethylenetetramine, and further preferably any one or a combination of at least two of 4-amino-2,3-dimethylazobenzene, 4-aminobiphenyl, aminoazobenzene, m-aminophenol, or p-aminophenol.

[0017] In the present invention, the amine curing agent preferably contains amine curing agents with more conjugated structures, such as aminoazobenzene, m-aminophenol, etc., because the conjugated structure reduces the energy gap through π-electron delocalization, causing the absorption wavelength of light to redshift, thereby enabling the material to have stronger visible light absorption ability.

[0018] Preferably, in the raw materials for preparing the photosensitive resin, the epoxy resin is 40 - 90 parts by weight (for example, it can be 40 parts by weight, 42 parts by weight, 45 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 55 parts by weight, 58 parts by weight, 60 parts by weight, 62 parts by weight, 65 parts by weight, 68 parts by weight, 70 parts by weight, 72 parts by weight, 75 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight, 85 parts by weight, 88 parts by weight, 90 parts by weight, etc.), and the amine curing agent is 10 - 30 parts by weight (for example, it can be 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, etc.).

[0019] Preferably, the preparation method of the photosensitive resin includes:

[0020] The epoxy resin reacts with the amine curing agent to obtain the photosensitive resin.

[0021] Preferably, the temperature of the reaction is 50 - 200 °C, for example, it can be 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, etc.

[0022] Preferably, the time of the reaction is 3 - 22 h, for example, it can be 3 h, 4 h, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, etc.

[0023] Preferably, the reaction is carried out in a first solvent.

[0024] Preferably, the first solvent includes any one or a combination of at least two of methyl acetate, ethyl acetate, butyl acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate or phenyl ethyl ether.

[0025] Preferably, the mass ratio of the first solvent to the epoxy resin is (0.5 - 3):1, for example, it can be 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, etc.

[0026] In the present invention, after the reaction is carried out in the first solvent, a solution containing the photosensitive resin can be obtained, which can be directly used for the preparation of the resin composition, and the first solvent contained in the solution is used as part of the organic solvent in the resin composition.

[0027] Preferably, the thermal acid generator includes any one or a combination of at least two of trifluoromethanesulfonate, hexafluorophosphate, p - toluenesulfonic acid or boron trifluoride ether complex.

[0028] Preferably, the trifluoromethanesulfonate includes any one or a combination of at least two of lithium trifluoromethanesulfonate, zinc trifluoromethanesulfonate or silver trifluoromethanesulfonate.

[0029] Preferably, the hexafluorophosphate includes any one or a combination of at least two of lithium hexafluorophosphate, zinc hexafluorophosphate or silver hexafluorophosphate.

[0030] Preferably, the boron trifluoride ether complex includes boron trifluoride - diethyl ether complex.

[0031] Preferably, the thermal acid generator includes any one or a combination of at least two of lithium hexafluorophosphate, lithium trifluoromethanesulfonate or boron trifluoride - diethyl ether complex.

[0032] Preferably, the resin composition further includes any one or a combination of at least two of a leveling agent, an antioxidant or a plasticizer.

[0033] Preferably, the leveling agent includes any one or a combination of at least two of silicone leveling agents, acrylate leveling agents, or fluorocarbon surfactants.

[0034] Preferably, the leveling agent includes any one or a combination of at least two of polyacrylate, polyether-modified polydimethylsiloxane, polyether silicone copolymer, or nonionic fluorocarbon surfactant.

[0035] Preferably, the amount of the leveling agent in the resin composition is 0.1 - 2 parts by weight, such as 0.1 part by weight, 0.2 part by weight, 0.4 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 part by weight, 1.4 part by weight, 1.6 part by weight, 1.8 part by weight, 2 part by weight, etc.

[0036] Preferably, the amount of the plasticizer in the resin composition is 1 - 5 parts by weight, such as 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight, 4.8 parts by weight, etc.

[0037] Preferably, the plasticizer includes butyl glycidyl ether and / or neopentyl glycol diglycidyl ether.

[0038] Preferably, the amount of the antioxidant in the resin composition is 0.5 - 2 parts by weight, such as 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, 1.1 part by weight, 1.2 part by weight, 1.3 part by weight, 1.4 part by weight, 1.5 part by weight, 1.6 part by weight, 1.7 part by weight, 1.8 part by weight, 1.9 part by weight, etc.

[0039] Preferably, the antioxidant includes 2,6 - di - tert - butyl - p - cresol and / or N - phenyl - β - naphthylamine.

[0040] Preferably, the resin composition further includes an organic solvent.

[0041] Preferably, the organic solvent includes any one or a combination of at least two of methyl acetate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or phenetole.

[0042] Preferably, the solid content of the resin composition is 5 - 40%, such as 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, etc.

[0043] Second aspect, the present invention provides a preparation method of the resin composition as described in the first aspect, the preparation method comprising:

[0044] Mixing a photosensitive resin and a thermal acid generator to obtain the resin composition.

[0045] Preferably, the mixed materials further include any one or a combination of at least two of an organic solvent, a leveling agent, an antioxidant or a plasticizer.

[0046] Preferably, the mixing temperature is 20 - 25°C, for example, it can be 20.2°C, 20.5°C, 20.8°C, 21°C, 21.2°C, 21.5°C, 21.8°C, 22°C, 22.5°C, 23°C, 23.5°C, 24°C, 24.5°C, etc.

[0047] Preferably, the mixing time is 6 - 18 h, for example, it can be 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, etc.

[0048] Preferably, the mixing method specifically includes:

[0049] Mixing the photosensitive resin with the organic solvent, adding the thermal acid generator, optionally the leveling agent, optionally the antioxidant and optionally the plasticizer to the obtained mixture, and mixing for 6 - 18 h under the condition of 20 - 25°C to obtain the resin composition.

[0050] Third aspect, the present invention provides a release layer, and the preparation raw materials of the release layer include the resin composition as described in the first aspect.

[0051] Preferably, the thickness of the release layer is 300 - 500 nm, for example, it can be 310 nm, 320 nm, 330 nm, 340 nm, 350 nm, 360 nm, 370 nm, 380 nm, 390 nm, 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, 460 nm, 470 nm, 480 nm, 490 nm, etc.

[0052] Fourth aspect, the present invention provides a preparation method of the release layer as described in the third aspect, the preparation method comprising:

[0053] Coating the resin composition as described in the first aspect on one surface of a substrate, and curing to obtain the release layer.

[0054] Preferably, the curing includes pre-curing and first curing carried out in sequence.

[0055] Preferably, the temperature of the pre-curing is 80-100°C, for example, it can be 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, etc.

[0056] Preferably, the time of the pre-curing is 4-8 min, for example, it can be 4.2 min, 4.5 min, 4.8 min, 5 min, 5.2 min, 5.5 min, 5.8 min, 6 min, 6.2 min, 6.5 min, 6.8 min, 7 min, 7.2 min, 7.5 min, 7.8 min, etc.

[0057] Preferably, the temperature of the first curing is 300-380°C, for example, it can be 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, etc.

[0058] Preferably, the time of the first curing is 10-30 min, for example, it can be 12 min, 14 min, 16 min, 18 min, 20 min, 22 min, 24 min, 26 min, 28 min, etc.

[0059] Preferably, the first curing is carried out in an air atmosphere.

[0060] Preferably, the substrate is a glass sheet.

[0061] In the fifth aspect, the present invention provides an application of the release layer as described in the third aspect in the processing of semiconductor devices.

[0062] Preferably, the semiconductor device includes a wafer.

[0063] The numerical ranges described in the present invention not only include the above-listed point values, but also include any point values between the above numerical ranges that are not listed. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the ranges.

[0064] Compared with the prior art, the present invention has the following beneficial effects:

[0065] The resin composition provided by the present invention does not contain fillers and can be used as a raw material for preparing a release layer. The formed release layer has a high absorption of 532-nm laser, the 532-nm light transmittance is 29.8-45.2%, the film surface of the release layer is smooth and uniform, the adhesion ability to the substrate is good, and the chemical resistance is good. Description of the Drawings

[0066] Figure 1 is a physical diagram of the release layer provided in Application Example 1;

[0067] Figure 2 is the thermogravimetric test curve of the release layer provided in Application Example 1;

[0068] Figure 3 is the light transmittance curve of the release layer provided in Application Example 3 under light irradiation of different wavelengths. Detailed Implementation Modes

[0069] The technical solution of the present invention will be further described below with reference to the accompanying drawings and through specific implementation modes. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0070] The sources of some components in the following embodiments and comparative examples are as described below:

[0071] (1) Polyethylene glycol diglycidyl ether: purchased from Liaoning Kelong Fine Chemical Co., Ltd., KF-200·400, epoxy equivalent of 350 g / mol;

[0072] (2) Bisphenol F epoxy resin: purchased from Guangzhou Yezeng Chemical Co., Ltd., NPEF-170, epoxy equivalent of 190 g / mol;

[0073] (3) Bisphenol A epoxy resin: purchased from Guangzhou Kaixin New Material Technology Co., Ltd., E44, epoxy equivalent of 170 g / mol;

[0074] (4) Polyether-modified polydimethylsiloxane: purchased from BYK Chemie, BYK378;

[0075] (5) Polyacrylate: purchased from Xintike Chemical, MAA;

[0076] (6) Nonionic fluorocarbon surfactant: purchased from Shenzhen Jintenglong Industry Co., Ltd., Capstone FS-3100.

[0077] Example 1

[0078] A resin composition, the components of the resin composition include 100 parts by weight of photosensitive resin A, 10 parts by weight of lithium hexafluorophosphate, 1 part by weight of polyether-modified polydimethylsiloxane, and propylene glycol methyl ether;

[0079] The preparation method of the photosensitive resin A includes:

[0080] Adding 60 parts by weight of polyethylene glycol diglycidyl ether, 10 parts by weight of bisphenol F epoxy resin, 10 parts by weight of bisphenol A epoxy resin, 20 parts by weight of aminoazobenzene, and 100 parts by weight of propylene glycol methyl ether into a reaction vessel, stirring at room temperature for 1 h, then heating to 100 °C, and maintaining at 100 °C for 22 h to obtain a solution containing the photosensitive resin A;

[0081] The preparation method of the resin composition includes:

[0082] Dilute the solution containing photosensitive resin A to 15% solid content with propylene glycol methyl ether, add 10 parts by weight of lithium hexafluorophosphate and 1 part by weight of polyether-modified polydimethylsiloxane, and stir at 25 °C for 6 h to obtain the resin composition.

[0083] Example 2

[0084] A resin composition, the components of the resin composition include 50 parts by weight of photosensitive resin B, 25 parts by weight of lithium trifluoromethanesulfonate, 0.1 part by weight of polyacrylate, 1 part by weight of butyl glycidyl ether, 0.7 part by weight of N-phenyl-β-naphthylamine, and propylene glycol methyl ether;

[0085] The preparation method of the photosensitive resin B includes:

[0086] Add 40 parts by weight of bisphenol A epoxy resin and 10 parts by weight of 4-amino-2,3-dimethylazobenzene to a reaction vessel and stir at room temperature for 1 h, then heat to 120 °C and hold at 120 °C for 5 h to obtain the photosensitive resin B;

[0087] The preparation method of the resin composition includes:

[0088] Mix propylene glycol methyl ether with the photosensitive resin B to obtain a solution with a solid content of 15%, add 25 parts by weight of lithium trifluoromethanesulfonate, 0.1 part by weight of polyacrylate, 1 part by weight of butyl glycidyl ether, and 0.7 part by weight of N-phenyl-β-naphthylamine thereto, and stir at 25 °C for 6 h to obtain the resin composition.

[0089] Example 3

[0090] A resin composition, the components of the resin composition include 120 parts by weight of photosensitive resin C, 40 parts by weight of boron trifluoride-ether complex, 2 parts by weight of nonionic fluorocarbon surfactant, and propylene glycol methyl ether;

[0091] The preparation method of the photosensitive resin C includes:

[0092] Add 90 parts by weight of polyethylene glycol diglycidyl ether and 30 parts by weight of 4-aminobiphenyl to a reaction vessel and stir at room temperature for 1 h, then heat to 120 °C and hold at 120 °C for 5 h to obtain the photosensitive resin C;

[0093] The preparation method of the resin composition includes:

[0094] Mix propylene glycol methyl ether with the photosensitive resin C to obtain a solution with a solid content of 15%. Add 40 parts by weight of boron trifluoride-ether complex and 2 parts by weight of nonionic fluorocarbon surfactant, and stir at 25 °C for 6 h to obtain the resin composition.

[0095] Example 4

[0096] A resin composition and its preparation method, the difference from Example 1 is only that the photosensitive resin A is replaced with the photosensitive resin D in equal mass, and the remaining raw materials, process parameters and steps are the same as those in Example 1;

[0097] The preparation method of the photosensitive resin D includes:

[0098] Add 60 parts by weight of polyethylene glycol diglycidyl ether, 10 parts by weight of bisphenol F epoxy resin, 10 parts by weight of bisphenol A epoxy resin, 20 parts by weight of toluidine and 100 parts by weight of propylene glycol methyl ether into a reaction vessel and stir at room temperature for 1 h, then heat to 100 °C and maintain at 100 °C for 22 h to obtain a solution containing the photosensitive resin D.

[0099] Example 5

[0100] A resin composition and its preparation method, the difference from Example 1 is only that lithium hexafluorophosphate is replaced with p-toluenesulfonic acid in equal mass, and the remaining raw materials, process parameters and steps are the same as those in Example 1.

[0101] Comparative Example 1

[0102] A resin composition and its preparation method, the difference from Example 1 is only that the photosensitive resin A is replaced with the photosensitive resin E in equal mass, and the remaining raw materials, process parameters and steps are the same as those in Example 1;

[0103] The preparation method of the photosensitive resin E includes:

[0104] Add 60 parts by weight of polyethylene glycol diglycidyl ether, 10 parts by weight of bisphenol F epoxy resin, 10 parts by weight of bisphenol A epoxy resin, 20 parts by weight of phthalic anhydride and 100 parts by weight of propylene glycol methyl ether into a reaction vessel and stir at room temperature for 1 h, then heat to 100 °C and maintain at 100 °C for 22 h to obtain a solution containing the photosensitive resin E.

[0105] Comparative Example 2

[0106] A resin composition and its preparation method, the difference from Example 1 is only that lithium hexafluorophosphate is not used, that is, the resin composition does not contain lithium hexafluorophosphate, and the remaining raw materials, process parameters and steps are the same as those in Example 1.

[0107] Comparative Example 3

[0108] A resin composition and its preparation method, which are only different from those in Example 1 in that the lithium hexafluorophosphate is 85 parts by weight, and the remaining raw materials, process parameters and steps are the same as those in Example 1.

[0109] Application Example 1

[0110] A release layer, the preparation raw materials of the release layer include the resin composition provided in Example 1, and the thickness of the release layer is 400 nm;

[0111] The preparation method of the release layer includes:

[0112] The resin composition provided in Example 1 was spin-coated on the surface of a glass sheet, and after pre-baking at 90 °C for 5 min and baking at 320 °C for 10 min, the release layer was obtained;

[0113] The physical picture of the release layer is as Figure 1 shown, from Figure 1 it can be seen that the surface of the release layer prepared by using the resin composition provided by the present invention is uniform and smooth.

[0114] Application Examples 2-5, Comparative Application Examples 1-3

[0115] A release layer and its preparation method, which are only different from those in Application Example 1 in that the resin composition provided in Example 1 is replaced with the resin compositions provided in Examples 2-5 and Comparative Examples 1-3, and the remaining process parameters and steps are the same as those in Application Example 1.

[0116] Performance Test

[0117] (1) 532 nm light transmittance: The light transmittance of the release layer at a wavelength of 532 nm was measured using a UV-Vis spectrophotometer, and the test results are shown in Table 1;

[0118] The light transmittance of the release layer provided in Application Example 3 under light of different wavelengths was measured using a UV-Vis spectrophotometer, and the test results are as Figure 3 shown, from Figure 3 it can be seen that the release layer provided by the present invention has a high absorption of light with a wavelength of 532 nm;

[0119] (2) Chemical resistance: The release layer was successively soaked in 10% H2SO3 solution, 5% KOH solution, NMP, and DMSO solvents at room temperature for 30 min, and then a profilometer (Bruker DektakXT profilometer, Germany) was used to measure the thickness of the film layer before and after soaking, and the corrosion thickness was calculated. The corrosion thickness = the thickness before soaking - the thickness after soaking;

[0120] The release layers provided in Application Examples 1-5 and Comparative Application Examples 1-3 were tested according to the above method, and the test results are shown in Table 1 below:

[0121] Table 1

[0122] 532 nm light transmittance (%) Etching thickness (nm) Application Example 1 33.1 0 Application Example 2 29.8 0 Application Example 3 32.6 0 Application Example 4 42.3 0 Application Example 5 45.2 0 Comparative Application Example 1 50.6 52 Comparative Application Example 2 60.2 350 Comparative Application Example 3 25.1 65

[0123] As can be seen from Table 1, compared with Comparative Application Examples 1-2, Application Examples 1-5 all have a lower visible light transmittance, and at the same time have strong chemical resistance, and have good tolerance to acid-base solutions and polar solvents, which can meet the requirements of various wet processes for chip packaging.

[0124] The light transmittance of the release layer provided by Application Example 4 is on the high side because the curing agent toluidine used in the release layer has fewer conjugated structures than aminoazobenzene, and the visible light absorption ability is poor.

[0125] It can be seen from Application Example 5 and Comparative Application Example 3 that the type and content of the thermal acid generator have great effects on both the light transmittance and chemical resistance of the release layer.

[0126] It can be seen from Comparative Application Example 2 that when the thermal acid generator is not added, the light transmittance of the release layer is very high and the chemical resistance is poor, because the thermal acid generator can promote the crosslinking and carbonization of the resin composition during the high-temperature curing process, thereby endowing the material with better chemical resistance and low light transmittance.

[0127] (3) Thermal stability: The release layer provided by Application Example 1 was tested using a TGA thermogravimetric analyzer (Nanjing Dazhan Instrument DZ-TGA101 thermogravimetric analyzer). The test steps were as follows: Scrape off the cured film layer of Application Example 1, prepare a sample and weigh 5 mg. After loading the sample, set the heating program to 10 °C / min, rise from room temperature to 115 °C, hold for 15 min to remove the moisture in the sample, and continue to rise to 800 °C at a heating rate of 10 °C / min. The test results are as Figure 2 shown. It can be Figure 2 seen that the release layer provided by the present invention has good thermal stability, and its 3% thermal weight loss temperature exceeds 300 °C, which can meet the requirements of the high-temperature process for chip packaging.

[0128] The applicant declares that the present invention uses the above embodiments to illustrate the resin composition of the present invention, its preparation method and application, but 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 improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A resin composition, characterized in that, The resin composition comprises the following components by weight: 50-120 parts by weight of a photosensitive resin and 10-40 parts by weight of a thermal acid generator; The raw materials for preparing the photosensitive resin include a combination of an epoxy resin and an amine curing agent.

2. The resin composition according to claim 1, characterized in that, The epoxy resin includes an aliphatic epoxy resin and / or an aromatic epoxy resin; Preferably, the epoxy resin includes any one or a combination of at least two of bisphenol A epoxy resin, bisphenol F epoxy resin, poly(1,4-butanediol diglycidyl ether), poly(propylene glycol diglycidyl ether), or poly(ethylene glycol diglycidyl ether); Preferably, the epoxy equivalent of the epoxy resin is 150-350 g / mol; Preferably, the amine curing agent includes any one or a combination of at least two of aminoazobenzene, 4-aminobiphenyl, 4-amino-2,3-dimethylazobenzene, aniline, toluidine, m-aminophenol, p-aminophenol, ethylenediamine, hexamethylenediamine, diethylenetriamine, or triethylenetetramine, and more preferably any one or a combination of at least two of 4-amino-2,3-dimethylazobenzene, 4-aminobiphenyl, aminoazobenzene, m-aminophenol, or p-aminophenol; Preferably, in the raw materials for preparing the photosensitive resin, the epoxy resin is 40-90 parts by weight and the amine curing agent is 10-30 parts by weight.

3. The resin composition according to claim 1 or 2, wherein The preparation method of the photosensitive resin includes: Reacting the epoxy resin with the amine curing agent to obtain the photosensitive resin; Preferably, the temperature of the reaction is 50-200 °C; Preferably, the time of the reaction is 3-22 h; Preferably, the reaction is carried out in a first solvent; Preferably, the first solvent includes any one or a combination of at least two of methyl acetate, ethyl acetate, butyl acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, or phenyl ethyl ether; Preferably, the mass ratio of the first solvent to the epoxy resin is (0.5-3):

1.

4. The resin composition according to any one of claims 1 to 3, characterized in that, The thermal acid generator includes any one or a combination of at least two of trifluoromethanesulfonate, hexafluorophosphate, p-toluenesulfonic acid, or boron trifluoride ether complex; Preferably, the trifluoromethanesulfonate includes any one or a combination of at least two of lithium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, or silver trifluoromethanesulfonate; Preferably, the hexafluorophosphate includes any one or a combination of at least two of lithium hexafluorophosphate, zinc hexafluorophosphate, or silver hexafluorophosphate; Preferably, the boron trifluoride ether complex includes boron trifluoride-ethyl ether complex; Preferably, the thermal acid generator includes any one or a combination of at least two of lithium hexafluorophosphate, lithium trifluoromethanesulfonate, or boron trifluoride-ethyl ether complex; Preferably, the resin composition further includes any one or a combination of at least two of a leveling agent, an antioxidant, or a plasticizer; Preferably, the leveling agent includes any one or a combination of at least two of silicone leveling agents, acrylate leveling agents, or fluorocarbon surfactants; Preferably, the leveling agent includes any one or a combination of at least two of polyacrylate, polyether-modified polydimethylsiloxane, polyether siloxane copolymer, or nonionic fluorocarbon surfactant; Preferably, the leveling agent in the resin composition is 0.1-2 parts by weight; Preferably, the plasticizer in the resin composition is 1-5 parts by weight; Preferably, the antioxidant in the resin composition is 0.5-2 parts by weight.

5. The resin composition according to any one of claims 1 to 4, characterized in that, The resin composition further comprises an organic solvent; Preferably, the organic solvent comprises any one or a combination of at least two of methyl acetate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or phenetole; Preferably, the solid content of the resin composition is 5-40%.

6. A method for preparing a resin composition according to any one of claims 1-5, characterized in that, The preparation method comprises: Mixing a photosensitive resin and a thermal acid generator to obtain the resin composition.

7. The preparation method according to claim 6, characterized in that, The mixed materials further comprise any one or a combination of at least two of an organic solvent, a leveling agent, an antioxidant or a plasticizer; Preferably, the mixing temperature is 20-25 °C; Preferably, the mixing time is 6-18 h.

8. A release layer, characterized in that, The raw materials for preparing the release layer include the resin composition according to any one of claims 1-5; Preferably, the thickness of the release layer is 300-500 nm.

9. A method for preparing a release layer as described in claim 8, characterized in that, The preparation method comprises: Coating the resin composition according to any one of claims 1-5 on one surface of a substrate, and curing to obtain the release layer; Preferably, the curing comprises pre-curing and first curing carried out in sequence; Preferably, the pre-curing temperature is 80-100 °C; Preferably, the pre-curing time is 4-8 min; Preferably, the first curing temperature is 300-380 °C; Preferably, the first curing time is 10-30 min.

10. Use of a release layer according to claim 8 in the processing of semiconductor devices; preferably, the semiconductor device comprises a wafer.

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