A film stripping adhesive tape for semiconductor processing and a preparation process thereof

Abstract

The application provides a film stripping adhesive tape for semiconductor processing and a preparation process thereof, and relates to the technical field of electronic adhesive preparation. The film stripping adhesive tape is prepared through the following steps: coating a PVODC solution on one side of a PET base film, drying to form a non-silicon release layer; mixing a hydroxyl polyester resin, an HDI trimer and ethyl acetate to coat the other side of the PET base film, and baking to form a primer layer; mixing hydroxyl-terminated polybutadiene, a polyester superdispersant and ethyl acetate to form a premix solution; mixing methylcyclohexane, ethyl acetate and propylene glycol methyl ether acetate, adding polyisobutylene, SIS and hydrogenated petroleum resin, and stirring to obtain a main glue solution; pouring the premix solution into the main glue solution, adding IPDI trimer and stannous octoate, stirring, defoaming, and then coating the composite glue solution on the surface of the primer layer to form a glue layer, and heating and curing to obtain the film stripping adhesive tape for semiconductor processing. The film stripping adhesive tape prepared by the application has good adhesion, unwinding and aging resistance.

Description

Technical Field

[0001] This invention relates to the field of electronic adhesive preparation technology, specifically to a semiconductor manufacturing process release tape and its preparation process. Background Technology

[0002] In semiconductor wafer manufacturing, wafer dicing, advanced packaging, and device transfer processes, release tapes are commonly used for temporary protection of wafer surfaces, dicing support, and inter-process transfer support. During use, these tapes need to possess both high initial tack and surface wetting capabilities to ensure rapid adhesion of the adhesive layer to the semiconductor substrate surface, and good peel cleanliness to avoid issues such as stringing and residue.

[0003] However, existing release tapes still have shortcomings in their structural design. The lack of an effective transition and anchoring structure between the adhesive layer and the base film makes them prone to interlayer delamination, localized peeling, or adhesive layer transfer during application, heating, or peeling. Furthermore, traditional release layers often use silicone-based systems, posing a risk of silicone contamination; and the aromatic hydrocarbon solvents such as toluene commonly used in existing processes also present problems of volatile residues and significant environmental burden. Moreover, without effective aging protection during storage and use, the tapes are susceptible to thermo-oxidative aging, hydrolytic degradation, and performance decline, thus affecting long-term reliability.

[0004] Furthermore, to improve the cohesion and stability of the adhesive layer, vulcanization systems or other crosslinking systems are introduced into the tape. For example, patent application CN117264583A discloses a method for preparing a high-viscosity hot-melt pressure-sensitive adhesive, including steps such as base material preparation, mixing treatment, obtaining a modified liquid, adding fillers, and curing. The base material includes plasticizers, thickeners, tackifiers, resins, vulcanized rubber compositions, vulcanizing agents, and accelerators. The crosslinking agent, accelerator, and the combination of the vulcanized rubber composition and vulcanizing agent improve the curing speed and storage stability of the hot-melt pressure-sensitive adhesive. However, the vulcanized rubber composition and vulcanizing agent used in this hot-melt pressure-sensitive adhesive affect the flexibility and wetting ability of the adhesive layer, thus affecting the tape's adhesion.

[0005] In summary, there is a need to provide a semiconductor manufacturing process release tape and its preparation process to solve the problems existing in the prior art. Summary of the Invention

[0006] In view of this, and in response to the problems of insufficient adhesion, poor adhesive layer flexibility, and easy residue in existing film-removing tapes, the present invention provides a film-removing tape for semiconductor manufacturing processes and its preparation process.

[0007] To achieve the above objectives, the present invention provides a semiconductor manufacturing process release tape and its preparation process, comprising the following steps: S1. A PVODC solution is coated on the non-coated side of a PET base film and dried to form a non-silicone release layer; a primer is prepared by mixing hydroxyl polyester resin, HDI trimer and ethyl acetate, and then coated onto the coated side of the PET base film and baked to form a primer layer. S2. Mix hydroxyl-terminated polybutadiene, polyester-type superdispersant and ethyl acetate to obtain a premix; mix methylcyclohexane, ethyl acetate and propylene glycol methyl ether acetate evenly, add polyisobutylene, SIS and hydrogenated petroleum resin, stir to dissolve and obtain the main adhesive solution; S3. Pour the premix into the main adhesive solution, add IPDI trimer and stannous octoate, and after stirring and degassing, obtain the composite adhesive solution. S4. Apply the composite adhesive to the surface of the base layer to form an adhesive layer, perform a three-stage heating treatment, and allow it to stand and mature to obtain a release tape for semiconductor manufacturing.

[0008] In this invention, polyisobutylene (PIB) and SIS (styrene-isoprene-styrene block copolymer) constitute the matrix of the composite adhesive. PIB improves the initial tack and surface wetting ability of the adhesive layer, while SIS improves the elasticity and film continuity of the adhesive layer. The combination of these two components allows the adhesive layer formed by the composite adhesive to adhere well to the semiconductor substrate surface while maintaining high adhesion. Furthermore, by introducing a premixed solution composed of hydroxyl-terminated polybutadiene (HTPB) and a polyester-type superdispersant into the main adhesive, and reacting it with IPDI trimer (alicyclic polyisocyanate) during a three-stage heating process, a dispersed polyurethane cross-linked structure is formed within the adhesive layer. This improves the cohesive stability of the adhesive layer while maintaining good flexibility and adhesion, which helps reduce problems such as stringing and residual adhesive during high-temperature peeling.

[0009] In this invention, a base coating comprising hydroxyl polyester resin and HDI trimer (isocyanate crosslinking agent) is applied to the adhesive-coated surface of a PET base film. The hydroxyl polyester resin exhibits good molecular compatibility with the PET base film, which is beneficial for improving the adhesion of the base coating to the PET base film surface. Simultaneously, the isocyanate groups in the HDI trimer not only crosslink with the base coating, improving its own stability, but also react with the hydroxyl-terminated polybutadiene (HTPB) in the adhesive layer during the subsequent three-stage drying and in-situ crosslinking process, thereby enhancing the bonding strength between the base coating and the adhesive layer. This allows the adhesive layer formed by the composite adhesive to adhere more firmly to the PET base film surface, reducing the risk of interlayer delamination and localized peeling during the peeling process.

[0010] This invention uses methylcyclohexane (MCH), ethyl acetate (EA), and propylene glycol methyl ether acetate (PMA) to form a mixed solvent system, which can replace the aromatic hydrocarbon solvents such as toluene commonly used in the preparation of traditional adhesives. This not only meets the dissolution and dispersion requirements of each component in the main adhesive and composite adhesive, but also helps to reduce the volatile residues caused by traditional solvents and reduce the environmental burden.

[0011] Optionally, the main adhesive also contains a primary antioxidant, a secondary antioxidant, and an anti-hydrolysis agent. The primary antioxidant is antioxidant 1010, the secondary antioxidant is dodecyl thiodipropionate, and the anti-hydrolysis agent is polycarbodiimide.

[0012] In this invention, a dual aging protection system is constructed by adding primary antioxidant 1010, secondary antioxidant di-dodecyl thiodipropionate (DLTDP), and anti-hydrolysis agent polycarbodiimide (Stabaxol P200) to the main adhesive. The primary antioxidant 1010 and the secondary antioxidant DLTDP work synergistically to inhibit thermo-oxidative aging of the adhesive layer during heating, storage, and use, thereby slowing down the performance degradation of the adhesive layer under high-temperature conditions. The polycarbodiimide Stabaxol P200 helps to slow down the degradation of the polyurethane cross-linked structure in the adhesive layer under humid and hot conditions, reducing the risk of structural deterioration and performance decline due to hydrolysis. Through the synergistic effect of this dual aging protection system, the adhesive layer formed by the composite adhesive can maintain good structural stability in thermo-oxidative and humid and hot environments, thus contributing to the long-term reliability of the peel-off tape.

[0013] Optionally, in step S1, after uniformly coating the non-coated surface of the PET base film with PVODC solution, it is heated to 90~100℃ and dried to form a non-silicone release layer; the concentration of the PVODC solution is 0.4~0.6wt%, the solute is polyoctadecylcarbamate, and the solvent is prepared by mixing methylcyclohexane and ethyl acetate in a weight ratio of (6.5~7.5):(2.5~3.5).

[0014] In this invention, a non-silicone release layer is formed by coating the non-coated surface of a PET base film with a polyoctadecyl polyurethane (PVODC) solution. This not only provides stable unwinding performance for the film-removing tape, but also avoids the silicon contamination problem caused by silicon-based release materials.

[0015] Optionally, in step S1, hydroxyl polyester resin, HDI trimer and ethyl acetate are added to a mixing tank and stirred at 300-400 rpm for 20-30 minutes at 20-30°C to obtain a primer. The primer is then uniformly coated onto the adhesive surface of the PET base film and heated to 75-85°C for 2-4 minutes to form a base coating layer. The thickness of the base coating layer is 0.4-0.6 μm.

[0016] Optionally, in step S2, hydroxyl-terminated polybutadiene, Solsperse 20000 polyester-type superdispersant, and ethyl acetate are added to a premix container and stirred at 200-300 rpm for 10-15 min to obtain a premix; methylcyclohexane, ethyl acetate, and propylene glycol methyl ether acetate are mixed and stirred at 80-120 rpm for 15-20 min; polyisobutylene, SIS, and hydrogenated petroleum resin are added sequentially, and the mixture is heated to 55-65°C and stirred at 70-90 rpm for 5-7 h to obtain the main adhesive solution.

[0017] Optionally, the main adhesive solution is cooled to 35~45℃, premixed solution is added, and stirred for 30~40min. IPDI trimer and stannous octoate are added, and stirring is continued for 15~20min. Vacuum degassing is performed to obtain the composite adhesive solution.

[0018] Optionally, the vacuum degree of the vacuum degassing is -0.098 to -0.095 MPa, and the time is 40 to 60 minutes.

[0019] In this invention, vacuum degassing effectively removes air bubbles and dissolved gases entrained in the composite adhesive, reducing the risk of air bubble defects during subsequent coating processes. This results in a denser and more uniform adhesive layer structure, reducing pinholes, voids, and localized stress concentrations.

[0020] Optionally, the three-stage heating treatment includes: the first stage: heating to 68~72℃ and holding at a constant temperature for 1.5~2.5 min; the second stage: heating to 90~95℃ and holding at a constant temperature for 1.5~2.5 min; and the third stage: heating to 115~120℃ and holding at a constant temperature for 2.5~3.5 min.

[0021] This invention employs a three-stage heating process to dry and in-situ crosslink the adhesive layer formed by the composite adhesive solution. Utilizing the differences in evaporation rates of ethyl acetate (EA), methylcyclohexane (MCH), and propylene glycol methyl ether acetate (PMA), each solvent evaporates sequentially at different temperature zones. This results in a more stable drying and film-forming process for the adhesive layer, reducing problems such as bubbles, surface defects, and uneven drying. It also provides conditions for adjusting the molecular chain segments within the system and forming crosslinked structures. Simultaneously, the third stage of heating promotes crosslinking between hydroxyl-terminated polybutadiene (HTPB) and IPDI trimer (alicyclic polyisocyanate), enhancing the bonding stability between the adhesive layer and the base layer.

[0022] The present invention also provides a release tape for semiconductor manufacturing processes, which is prepared by the above-described process for preparing a release tape for semiconductor manufacturing processes. The primer comprises the following raw materials in parts by weight: 2.5-3.5 parts of hydroxyl polyester resin, 0.8-1.2 parts of HDI trimer, and 95-96 parts of ethyl acetate; the composite adhesive comprises the following raw materials in parts by weight: 27-34 parts of premix, 330-365 parts of main adhesive, 1.3-1.6 parts of IPDI trimer, and 0.04-0.06 parts of stannous octoate; the main adhesive comprises the following raw materials in parts by weight: 147-152 parts of methylcyclohexane, 53-58 parts of ethyl acetate, 20-30 parts of propylene glycol methyl ether acetate, 29-32 parts of polyisobutylene, 47-51 parts of SIS, and 37-44 parts of hydrogenated petroleum resin.

[0023] Optionally, the main adhesive solution may also contain the following raw materials in parts by weight: antioxidant 1010 0.8-1.2 parts, disodecyl thiodipropionate 0.16-0.23 parts, and polycarbodiimide 0.28-0.31 parts; the premixed solution may contain the following raw materials in parts by weight: hydroxyl-terminated polybutadiene 9-11 parts, Solsperse 20000 polyester-type superdispersant 0.17-0.21 parts, and ethyl acetate 18-22 parts.

[0024] The above-described technical solution of the present invention has at least the following beneficial effects: In this invention, polyisobutylene and SIS constitute the matrix of the composite adhesive, and their combination gives the adhesive layer good initial tack, wetting ability, elasticity, and film-forming continuity. By introducing a premixed liquid composed of hydroxyl-terminated polybutadiene and a polyester-type superdispersant, and reacting it with IPDI trimer during a three-stage heating process, a dispersed polyurethane crosslinked structure is formed inside the adhesive layer. This improves cohesive stability while maintaining flexibility and adhesion properties, and reduces stringing and residual adhesive during high-temperature peeling.

[0025] In this invention, a base coating comprising hydroxyl polyester resin and HDI trimer is applied to the adhesive-coated surface of a PET base film. The hydroxyl polyester resin has good compatibility with the PET base film, improving the adhesion of the base coating; the HDI trimer participates in the crosslinking of the base coating and reacts with the terminal hydroxyl polybutadiene in the adhesive layer during subsequent heat treatment, enhancing the bonding strength between the base coating and the adhesive layer and reducing the risk of interlayer delamination and peeling during the peeling process.

[0026] This invention uses a mixed solvent system consisting of methylcyclohexane, ethyl acetate, and propylene glycol methyl ether acetate to replace traditional aromatic hydrocarbon solvents such as toluene, thereby meeting the dissolution and dispersion requirements of each component while reducing solvent volatilization residues and environmental burden. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. The described embodiments are some embodiments of the present invention, and all other embodiments obtained by those skilled in the art based on the described embodiments of the present invention are within the scope of protection of the present invention.

[0028] Example 1 A 50 μm thick PET base film is placed on a roll-to-roll coating machine, and a PVODC solution is coated on the non-coated side of the PET base film using a microgravure plate. The concentration of the PVODC solution is 0.6 wt%, the solute is polyoctadecylcarbamate, and the solvent is prepared by mixing methylcyclohexane (MCH) and ethyl acetate (EA) in a weight ratio of 7.5:3.5. After coating, it is dried at 100°C to form a non-silicone release layer.

[0029] 3.5 parts of hydroxyl polyester resin, 1.2 parts of HDI trimer and 96 parts of ethyl acetate (EA) were added to a mixing tank and stirred at 400 rpm for 30 min at 30 °C to obtain a primer. The primer was then evenly coated onto the adhesive surface of the PET base film and baked at 85 °C for 4 min to form a primer layer with a thickness of 0.6 μm.

[0030] Mix 11 parts of hydroxyl-terminated polybutadiene (HTPB), 0.21 parts of Solsperse 20000 polyester superdispersant and 22 parts of ethyl acetate (EA), and stir at 300 rpm for 15 min until the solution is uniform and transparent to obtain a premix. Add 152 parts of methylcyclohexane (MCH), 58 parts of ethyl acetate (EA), and 30 parts of propylene glycol methyl ether acetate (PMA) to a mixing tank and stir at 120 rpm for 20 min. Then add 32 parts of polyisobutylene (PIB), 51 parts of styrene-isoprene-styrene block copolymer (SIS), 44 parts of hydrogenated petroleum resin, 1.2 parts of primary antioxidant 1010, 0.23 parts of secondary antioxidant disodecyl thiodipropionate (DLTDP), and 0.31 parts of anti-hydrolysis agent polycarbodiimide (Stabaxol P200). Heat to 65°C and stir at 90 rpm for 7 h until all components are completely dissolved and a viscous transparent adhesive solution is formed, thus obtaining the main adhesive solution.

[0031] Cool the main adhesive solution to 45°C, slowly add the premixed solution while stirring, continue stirring for 40 minutes, add 1.6 parts of IPDI trimer and 0.06 parts of stannous octoate (T-9) catalyst, continue stirring for 20 minutes, evacuate to -0.095MPa for 60 minutes, and then restore to atmospheric pressure to obtain the composite adhesive solution.

[0032] The composite adhesive is evenly applied to the surface of the PET base film's undercoat to form an adhesive layer, and then placed in a hot air oven for a three-stage heating treatment. Stage 1: Heating to 72℃ and holding for 2.5 minutes; Stage 2: Heating to 95℃ and holding for 2.5 minutes; Stage 3: Heating further to 120℃ and holding for 3.5 minutes; Finally, the film is cured at 30℃ for 84 hours to obtain a release tape for semiconductor manufacturing.

[0033] Example 2 A 50 μm thick PET base film is placed on a roll-to-roll coating machine, and a PVODC solution is coated on the non-coated side of the PET base film using a microgravure plate. The concentration of the PVODC solution is 0.5 wt%, the solute is polyoctadecylcarbamate, and the solvent is prepared by mixing methylcyclohexane (MCH) and ethyl acetate (EA) in a weight ratio of 7:3. After coating, it is dried at 95°C to form a non-silicone release layer.

[0034] Add 3 parts of hydroxyl polyester resin, 1.1 parts of HDI trimer and 95.5 parts of ethyl acetate (EA) to a mixing tank and stir at 350 rpm for 25 min at 25 °C to obtain a primer liquid; then coat the primer liquid evenly on the adhesive surface of the PET base film and bake at 82 °C for 3 min to form a primer layer with a thickness of 0.45 μm.

[0035] Mix 10 parts of hydroxyl-terminated polybutadiene (HTPB), 0.2 parts of Solsperse 20000 polyester superdispersant and 20 parts of ethyl acetate (EA), and stir at 250 rpm for 12 min until the solution is uniform and transparent to obtain a premix. Add 150 parts of methylcyclohexane (MCH), 55 parts of ethyl acetate (EA), and 25 parts of propylene glycol methyl ether acetate (PMA) to a mixing tank and stir at 100 rpm for 15 min. Then add 30 parts of polyisobutylene (PIB), 48 parts of styrene-isoprene-styrene block copolymer (SIS), 39 parts of hydrogenated petroleum resin, 0.9 parts of primary antioxidant 1010, 0.2 parts of secondary antioxidant disodecyl thiodipropionate (DLTDP), and 0.3 parts of anti-hydrolysis agent polycarbodiimide (Stabaxol P200). Heat to 60°C and stir at 80 rpm for 6 h until all components are completely dissolved and a viscous transparent adhesive solution is formed, thus obtaining the main adhesive solution.

[0036] Cool the main adhesive solution to 40°C, slowly add the premixed solution while stirring, continue stirring for 30 minutes, add 1.5 parts of IPDI trimer and 0.05 parts of stannous octoate (T-9) catalyst, continue stirring for 18 minutes, evacuate to -0.096 MPa for 50 minutes, and then restore to atmospheric pressure to obtain the composite adhesive solution.

[0037] The composite adhesive is evenly applied to the surface of the PET base film's undercoat to form an adhesive layer, and then placed in a hot air oven for a three-stage heating treatment. The first stage involves heating to 70℃ and holding for 2 minutes; the second stage involves heating to 92℃ and holding for 2 minutes; the third stage involves further heating to 118℃ and holding for 3 minutes; and finally, the material is cured at 25℃ for 72 hours to obtain a release tape for semiconductor manufacturing.

[0038] Example 3 A 50 μm thick PET base film is placed on a roll-to-roll coating machine, and a PVODC solution is coated on the non-coated side of the PET base film using a microgravure plate. The concentration of the PVODC solution is 0.4 wt%, the solute is polyoctadecylcarbamate, and the solvent is prepared by mixing methylcyclohexane (MCH) and ethyl acetate (EA) in a weight ratio of 6.5:2.5. After coating, it is dried at 90 °C to form a non-silicone release layer.

[0039] 2.5 parts of hydroxyl polyester resin, 0.8 parts of HDI trimer and 95 parts of ethyl acetate (EA) were added to a mixing tank and stirred at 300 rpm for 20 min at 20 °C to obtain a primer. The primer was then evenly coated onto the adhesive surface of the PET base film and baked at 75 °C for 2 min to form a primer layer with a thickness of 0.4 μm.

[0040] Nine parts of hydroxyl-terminated polybutadiene (HTPB), 0.17 parts of Solsperse 20000 polyester superdispersant, and 18 parts of ethyl acetate (EA) were mixed and stirred at 200 rpm for 10 minutes until the solution was uniform and transparent, thus obtaining the premixed solution. Add 147 parts of methylcyclohexane (MCH), 53 parts of ethyl acetate (EA), and 20 parts of propylene glycol methyl ether acetate (PMA) to a mixing tank and stir at 80 rpm for 15 min. Then add 29 parts of polyisobutylene (PIB), 47 parts of styrene-isoprene-styrene block copolymer (SIS), 37 parts of hydrogenated petroleum resin, 0.8 parts of primary antioxidant 1010, 0.16 parts of secondary antioxidant disodecyl thiodipropionate (DLTDP), and 0.28 parts of hydrolysis inhibitor polycarbodiimide (Stabaxol P200). Heat to 55°C and stir at 70 rpm for 5 h until all components are completely dissolved and a viscous transparent adhesive solution is formed, thus obtaining the main adhesive solution.

[0041] Cool the main adhesive solution to 35°C, slowly add the premixed solution while stirring, continue stirring for 30 minutes, add 1.3 parts of IPDI trimer and 0.04 parts of stannous octoate (T-9) catalyst, continue stirring for 15 minutes, evacuate to -0.098MPa for 40 minutes, and then restore to atmospheric pressure to obtain the composite adhesive solution.

[0042] The composite adhesive is evenly applied to the surface of the PET base film's undercoat to form an adhesive layer, and then placed in a hot air oven for a three-stage heating treatment. Stage 1: Heating to 68℃ and holding for 1.5 minutes; Stage 2: Heating to 90℃ and holding for 1.5 minutes; Stage 3: Heating further to 115℃ and holding for 2.5 minutes; Finally, the film is cured at 20℃ for 60 hours to obtain a release tape for semiconductor manufacturing.

[0043] Example 4 A 50 μm thick PET base film is placed on a roll-to-roll coating machine, and a PVODC solution is coated on the non-coated side of the PET base film using a microgravure plate. The concentration of the PVODC solution is 0.6 wt%, the solute is polyoctadecylcarbamate, and the solvent is prepared by mixing methylcyclohexane (MCH) and ethyl acetate (EA) in a weight ratio of 7.5:3.5. After coating, it is dried at 100°C to form a non-silicone release layer.

[0044] 3.5 parts of hydroxyl polyester resin, 1.2 parts of HDI trimer and 96 parts of ethyl acetate (EA) were added to a mixing tank and stirred at 400 rpm for 30 min at 30 °C to obtain a primer. The primer was then evenly coated onto the adhesive surface of the PET base film and baked at 85 °C for 4 min to form a primer layer with a thickness of 0.6 μm.

[0045] 11 parts of hydroxyl-terminated polybutadiene (HTPB), 0.21 parts of Solsperse 20000 polyester-type superdispersant, and 22 parts of ethyl acetate (EA) were mixed and stirred at 300 rpm for 15 min until the solution was uniform and transparent, thus obtaining the premix. 152 parts of methylcyclohexane (MCH), 58 parts of ethyl acetate (EA), and 30 parts of propylene glycol methyl ether acetate (PMA) were added to the mixing tank and stirred at 120 rpm for 20 min. Then, 32 parts of polyisobutylene (PIB), 51 parts of styrene-isoprene-styrene block copolymer (SIS), and 44 parts of hydrogenated petroleum resin were added sequentially. The mixture was heated to 65°C and stirred at 90 rpm for 7 h until all components were completely dissolved and a viscous, transparent adhesive solution was formed, thus obtaining the main adhesive solution.

[0046] Cool the main adhesive solution to 45°C, slowly add the premixed solution while stirring, continue stirring for 40 minutes, add 1.6 parts of IPDI trimer and 0.06 parts of stannous octoate (T-9) catalyst, continue stirring for 20 minutes, evacuate to -0.095MPa for 60 minutes, and then restore to atmospheric pressure to obtain the composite adhesive solution.

[0047] The composite adhesive is evenly applied to the surface of the PET base film's undercoat to form an adhesive layer, and then placed in a hot air oven for a three-stage heating treatment. Stage 1: Heating to 72℃ and holding for 2.5 minutes; Stage 2: Heating to 95℃ and holding for 2.5 minutes; Stage 3: Heating further to 120℃ and holding for 3.5 minutes; Finally, the film is cured at 30℃ for 84 hours to obtain a release tape for semiconductor manufacturing.

[0048] Example 5 A 50 μm thick PET base film is placed on a roll-to-roll coating machine, and a PVODC solution is coated on the non-coated side of the PET base film using a microgravure plate. The concentration of the PVODC solution is 0.5 wt%, the solute is polyoctadecylcarbamate, and the solvent is prepared by mixing methylcyclohexane (MCH) and ethyl acetate (EA) in a weight ratio of 7:3. After coating, it is dried at 95°C to form a non-silicone release layer.

[0049] Add 3 parts of hydroxyl polyester resin, 1.1 parts of HDI trimer and 95.5 parts of ethyl acetate (EA) to a mixing tank and stir at 350 rpm for 25 min at 25 °C to obtain a primer liquid; then coat the primer liquid evenly on the adhesive surface of the PET base film and bake at 82 °C for 3 min to form a primer layer with a thickness of 0.45 μm.

[0050] 10 parts of hydroxyl-terminated polybutadiene (HTPB), 0.2 parts of Solsperse 20000 polyester-type superdispersant, and 20 parts of ethyl acetate (EA) were mixed and stirred at 250 rpm for 12 min until the solution was uniform and transparent, thus obtaining the premix. 150 parts of methylcyclohexane (MCH), 55 parts of ethyl acetate (EA), and 25 parts of propylene glycol methyl ether acetate (PMA) were added to the mixing tank and stirred at 100 rpm for 15 min. Then, 30 parts of polyisobutylene (PIB), 48 parts of styrene-isoprene-styrene block copolymer (SIS), and 39 parts of hydrogenated petroleum resin were added sequentially. The mixture was heated to 60°C and stirred at 80 rpm for 6 h until all components were completely dissolved and a viscous, transparent adhesive solution was formed, thus obtaining the main adhesive solution.

[0051] Cool the main adhesive solution to 40°C, slowly add the premixed solution while stirring, continue stirring for 30 minutes, add 1.5 parts of IPDI trimer and 0.05 parts of stannous octoate (T-9) catalyst, continue stirring for 18 minutes, evacuate to -0.096 MPa for 50 minutes, and then restore to atmospheric pressure to obtain the composite adhesive solution.

[0052] The composite adhesive is evenly applied to the surface of the PET base film's undercoat to form an adhesive layer, and then placed in a hot air oven for a three-stage heating treatment. The first stage involves heating to 70℃ and holding for 2 minutes; the second stage involves heating to 92℃ and holding for 2 minutes; the third stage involves further heating to 118℃ and holding for 3 minutes; and finally, the material is cured at 25℃ for 72 hours to obtain a release tape for semiconductor manufacturing.

[0053] Example 6 A 50 μm thick PET base film is placed on a roll-to-roll coating machine, and a PVODC solution is coated on the non-coated side of the PET base film using a microgravure plate. The concentration of the PVODC solution is 0.4 wt%, the solute is polyoctadecylcarbamate, and the solvent is prepared by mixing methylcyclohexane (MCH) and ethyl acetate (EA) in a weight ratio of 6.5:2.5. After coating, it is dried at 90 °C to form a non-silicone release layer.

[0054] 2.5 parts of hydroxyl polyester resin, 0.8 parts of HDI trimer and 95 parts of ethyl acetate (EA) were added to a mixing tank and stirred at 300 rpm for 20 min at 20 °C to obtain a primer. The primer was then evenly coated onto the adhesive surface of the PET base film and baked at 75 °C for 2 min to form a primer layer with a thickness of 0.4 μm.

[0055] Nine parts of hydroxyl-terminated polybutadiene (HTPB), 0.17 parts of Solsperse 20000 polyester-type superdispersant, and 18 parts of ethyl acetate (EA) were mixed and stirred at 200 rpm for 10 min until the solution was uniform and transparent, thus obtaining the premix. 147 parts of methylcyclohexane (MCH), 53 parts of ethyl acetate (EA), and 20 parts of propylene glycol methyl ether acetate (PMA) were added to the mixing tank and stirred at 80 rpm for 15 min. Then, 29 parts of polyisobutylene (PIB), 47 parts of styrene-isoprene-styrene block copolymer (SIS), and 37 parts of hydrogenated petroleum resin were added sequentially. The mixture was heated to 55°C and stirred at 70 rpm for 5 h until all components were completely dissolved and a viscous, transparent adhesive solution was formed, thus obtaining the main adhesive solution.

[0056] Cool the main adhesive solution to 35°C, slowly add the premixed solution while stirring, continue stirring for 30 minutes, add 1.3 parts of IPDI trimer and 0.04 parts of stannous octoate (T-9) catalyst, continue stirring for 15 minutes, evacuate to -0.098MPa for 40 minutes, and then restore to atmospheric pressure to obtain the composite adhesive solution.

[0057] The composite adhesive is evenly applied to the surface of the PET base film's undercoat to form an adhesive layer, and then placed in a hot air oven for a three-stage heating treatment. Stage 1: Heating to 68℃ and holding for 1.5 minutes; Stage 2: Heating to 90℃ and holding for 1.5 minutes; Stage 3: Heating further to 115℃ and holding for 2.5 minutes; Finally, the film is cured at 20℃ for 60 hours to obtain a release tape for semiconductor manufacturing.

[0058] The present invention also includes comparative examples and related experiments.

[0059] Comparative Example 1 The only difference from Example 1 is that no terminal hydroxyl polybutadiene was added; all other components and preparation steps were exactly the same, resulting in a semiconductor process release tape.

[0060] Comparative Example 2 The only difference from Example 1 is that HDI trimer was not added; all other components and preparation steps were exactly the same, resulting in a semiconductor process release tape.

[0061] Comparative Example 3 The only difference from Example 1 is that IPDI trimer was not added; all other components and preparation steps were exactly the same, resulting in a semiconductor process release tape.

[0062] Performance testing: The adhesion properties of the semiconductor process release tapes prepared in Examples 1-6 and Comparative Examples 1-3 were tested according to the national standard GB / T 4852-2002 "Test Method for Initial Tack of Pressure-Sensitive Adhesive Tapes" (the initial tack performance was evaluated by rolling a steel ball over an inclined groove and measuring the rolling distance d on the adhesive surface of the tape on a horizontal plate). The peel strength T was tested according to the national standard GB / T 2792-2014 "Test Method for Peel Strength of Adhesive Tapes". The test results are shown in Table 1.

[0063] The unwinding performance of the semiconductor process release tapes prepared in Examples 1-6 and Comparative Examples 1-3 was tested according to the national standard GB / T4850-2002 "Determination of Low-Speed ​​Unwinding Strength of Pressure-Sensitive Adhesive Tapes". The test results are shown in Table 1.

[0064] The residual adhesive removal properties of the semiconductor process release tapes prepared in Examples 1-6 and Comparative Examples 1-3 were tested. A 12mm × 110mm tape was cut, pressed onto an alumina ceramic plate, and held at a pressure of 0.25MPa for 10s. The tape was then stretched and removed at a speed of 300mm / min (ambient temperature 80℃, relative humidity 50%RH, stretching angle 30°). The presence of stringing or residual adhesive was observed and recorded. The test results are shown in Table 1.

[0065] The aging resistance of the semiconductor process release tapes prepared in Examples 1-6 and Comparative Examples 1-3: The tape samples were placed in a constant temperature and humidity chamber (ambient temperature 40℃, relative humidity 85%RH) for 200 hours, then removed and allowed to stand at room temperature for 2 hours. The peel strength T was then tested according to the national standard GB / T 2792-2014 "Test Method for Peel Strength of Adhesive Tapes". 老化 The test results are shown in Table 1.

[0066] Table 1

[0067] Based on the test results in Table 1, it can be seen that the rolling distance d of the semiconductor process release tapes prepared in Examples 1-6 is all within the range of 25-30 mm, the peel strength T is within the range of 22.7-26.8 N / 25 mm, the unwinding strength is between 3.6-3.8 N / 25 mm, and the peel strength T after aging is... 老化 The tensile strength is between 15.8 and 23.5 N / 25 mm, with no stringing or residue. This indicates that the semiconductor process release tape prepared by this invention possesses both good initial tack and unwinding properties, as well as good peel cleanliness and aging resistance.

[0068] Compared to Examples 4-6, Examples 1-3 added antioxidant 1010, auxiliary antioxidant DLTDP, and anti-hydrolysis agent polycarbodiimide to the main adhesive solution. According to the test results in Table 1, the peel strength T of Examples 1-3... 老化 The decrease was relatively small. This indicates that adding antioxidant 1010, auxiliary antioxidant DLTDP, and anti-hydrolysis agent polycarbodiimide to the main adhesive can inhibit the hydrolytic degradation of the adhesive layer under humid and hot conditions, thereby improving the aging resistance and long-term reliability of the film-removing tape.

[0069] Compared to Example 1, Comparative Example 1 without hydroxyl-terminated polybutadiene (HTPB) showed an increased rolling distance d to 72 mm, and improved peel strength T and peel strength after aging. 老化 The peel strength T1 decreased significantly, and stringing and residual adhesive were observed, indicating that the lack of HTPB in the formation of the polyurethane cross-linking structure resulted in insufficient cohesion in the adhesive layer, making it prone to cohesive failure during peeling and causing residual adhesive. Compared to Example 1, Comparative Example 2 did not add HDI trimer, resulting in decreased adhesion between the undercoat layer and the PET base film and adhesive layer, and its peel strength T1 and peel strength T2 decreased. 老化 All showed a decrease, and residual adhesive appeared; compared with Example 1, Comparative Example 3, which did not add IPDI trimer, had an increased rolling distance d, a decreased peel strength T, and a lower peel strength T after aging. 老化Further reduction, along with the appearance of stringing and residual adhesive, indicates that an effective cross-linked network structure has not been formed inside the adhesive layer, resulting in a soft system with insufficient cohesion, which easily leads to stringing and residual adhesive during the peeling process.

[0070] The above are preferred embodiments of the present invention. Those skilled in the art can make several improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A process for preparing a release tape for semiconductor manufacturing, characterized in that, The preparation steps include the following: S1. A PVODC solution is uniformly coated on the non-coated surface of a PET base film, and then heated to 90~100℃ and dried to form a non-silicone release layer. The concentration of the PVODC solution is 0.4~0.6wt%, the solute is polyoctadecylurethane, and the solvent is prepared by mixing methylcyclohexane and ethyl acetate in a weight ratio of (6.5~7.5):(2.5~3.5). A primer is prepared by mixing hydroxyl polyester resin, HDI trimer and ethyl acetate, and then coated onto the coated surface of the PET base film. After baking, a base layer is formed. S2. Mix and stir hydroxyl-terminated polybutadiene, polyester-type superdispersant and ethyl acetate to obtain a premix; Methylcyclohexane, ethyl acetate and propylene glycol methyl ether acetate were mixed evenly, and polyisobutylene, SIS and hydrogenated petroleum resin were added. After stirring and dissolving, the main adhesive solution was obtained. S3. Pour the premix into the main adhesive solution, add IPDI trimer and stannous octoate, and after stirring and degassing, obtain the composite adhesive solution. S4. Apply the composite adhesive liquid to the surface of the base layer to form an adhesive layer, perform a three-stage heating treatment, and allow it to stand and mature to obtain a semiconductor process release tape. The three-stage heating process includes: Stage 1: heating to 68~72℃ and holding for 1.5~2.5 minutes; Stage 2: heating to 90~95℃ and holding for 1.5~2.5 minutes; Stage 3: heating to 115~120℃ and holding for 2.5~3.5 minutes.

2. The preparation process of a semiconductor manufacturing peel-off tape according to claim 1, characterized in that, The main adhesive also contains a primary antioxidant, a secondary antioxidant, and an anti-hydrolysis agent. The primary antioxidant is antioxidant 1010, the secondary antioxidant is dodecyl thiodipropionate, and the anti-hydrolysis agent is polycarbodiimide.

3. The preparation process of a semiconductor manufacturing peel-off tape according to claim 1, characterized in that, In step S1, hydroxyl polyester resin, HDI trimer and ethyl acetate are added to a mixing tank and stirred at 300-400 rpm for 20-30 minutes at 20-30°C to obtain a primer. The primer is then uniformly coated onto the adhesive surface of the PET base film and heated to 75-85°C for 2-4 minutes to form a base coating layer. The thickness of the base coating layer is 0.4-0.6 μm.

4. The preparation process of a semiconductor manufacturing peel-off tape according to claim 1, characterized in that, In step S2, hydroxyl-terminated polybutadiene, Solsperse 20000 polyester-type superdispersant, and ethyl acetate are added to a premix container and stirred at 200-300 rpm for 10-15 min to obtain a premix; methylcyclohexane, ethyl acetate, and propylene glycol methyl ether acetate are mixed and stirred at 80-120 rpm for 15-20 min; polyisobutylene, SIS, and hydrogenated petroleum resin are added sequentially, and the mixture is heated to 55-65°C and stirred at 70-90 rpm for 5-7 h to obtain the main adhesive solution.

5. The preparation process of a semiconductor manufacturing peel-off tape according to claim 4, characterized in that, Cool the main adhesive solution to 35~45℃, add the premixed solution, stir for 30~40min, add IPDI trimer and stannous octoate, continue stirring for 15~20min, degas under vacuum to obtain the composite adhesive solution.

6. The preparation process of a semiconductor manufacturing peel-off tape according to claim 5, characterized in that, The vacuum degassing process is performed at a vacuum level of -0.098 to -0.095 MPa for a time of 40 to 60 minutes.

7. A semiconductor process release tape, manufactured using the process described in any one of claims 1 to 6, characterized in that, The primer comprises the following raw materials in parts by weight: 2.5-3.5 parts of hydroxyl polyester resin, 0.8-1.2 parts of HDI trimer, and 95-96 parts of ethyl acetate; The composite adhesive comprises the following raw materials in parts by weight: 27-34 parts of premix, 330-365 parts of main adhesive, 1.3-1.6 parts of IPDI trimer, and 0.04-0.06 parts of stannous octoate; The main adhesive comprises the following raw materials in parts by weight: 147-152 parts of methylcyclohexane, 53-58 parts of ethyl acetate, 20-30 parts of propylene glycol methyl ether acetate, 29-32 parts of polyisobutylene, 47-51 parts of SIS and 37-44 parts of hydrogenated petroleum resin.

8. The semiconductor manufacturing process peel-off tape according to claim 7, characterized in that, The main adhesive solution also contains the following raw materials in parts by weight: antioxidant 1010 0.8~1.2 parts, disodecyl thiodipropionate 0.16~0.23 parts, and polycarbodiimide 0.28~0.31 parts; The premix comprises the following raw materials in parts by weight: 9-11 parts of hydroxyl-terminated polybutadiene, 0.17-0.21 parts of Solsperse 20000 polyester-type superdispersant, and 18-22 parts of ethyl acetate.

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