High-cleanliness film uncovering adhesive tape for semiconductor manufacturing process and preparation process of high-cleanliness film uncovering adhesive tape

Abstract

The invention relates to the technical field of adhesive materials, and particularly discloses a high-cleanliness film uncovering adhesive tape for a semiconductor manufacturing process and a preparation process of the high-cleanliness film uncovering adhesive tape. The invention discloses a high-cleanliness film uncovering adhesive tape for a semiconductor manufacturing process. The high-cleanliness film uncovering adhesive tape comprises a PET film layer, a release layer and an adhesive layer, the release layer is prepared from the following raw materials: a fluorine-containing polyether-organic silicon grafted copolymer, nano titanium dioxide and potassium perfluorobutanesulfonate; the adhesive layer is prepared from the following raw materials: 40 to 60 parts of acrylate, 30 to 50 parts of polyurethane, 10 to 20 parts of methylbenzene, 5 to 8 parts of diisocyanate, 3 to 5 parts of dibenzoyl peroxide, 10 to 20 parts of rubber particles, 5 to 9 parts of quaternary ammonium salt modified montmorillonite, 10 to 20 parts of poly (vinyl cinnamate), 1 to 3 parts of photoinitiator and 3 to 8 parts of polyvinyl butyral. According to the high-cleanliness film uncovering adhesive disclosed by the invention, the release layer and the adhesive layer with special components are arranged, so that the adhesive tape has the advantages of high viscosity, easiness in unwinding, no residual adhesive and high cleanliness at the same time.

Description

Technical Field

[0001] This application relates to the field of adhesive materials technology, and more specifically, to a high-cleanliness peel-off tape for semiconductor manufacturing processes and its preparation process. Background Technology

[0002] In semiconductor manufacturing processes, release tape plays a crucial role. Semiconductor manufacturing involves numerous delicate and complex steps, from initial wafer processing to final chip packaging, each demanding stringent requirements for operational precision and material quality. Release tape is primarily used to accurately remove protective films and temporary adhesive layers from wafers or other semiconductor components at specific process stages. Its performance directly impacts the quality of semiconductor products, production efficiency, and process stability. For example, in wafer dicing and chip packaging, release tape needs to precisely peel off protective films to avoid damage or contamination of the wafer surface, ensuring the electrical performance and reliability of semiconductor components. Therefore, developing high-performance release tapes suitable for semiconductor manufacturing processes is of great significance for promoting the development of the semiconductor industry.

[0003] Currently, various release tapes for semiconductor manufacturing processes are available in existing technologies. These tapes typically employ specific substrate and adhesive formulations to meet the fundamental requirements of semiconductor manufacturing. Common substrates include polyethylene terephthalate (PET) and polyvinyl chloride (PVC), which possess a certain strength and flexibility to adapt to various operating environments. For adhesives, acrylic and rubber-based materials are commonly used, with the tape's tackiness controlled by adjusting the formulation ratios. Some release tapes enhance the adhesion between the adhesive and substrate by optimizing substrate surface treatment processes, thereby improving the overall performance of the tape. Simultaneously, some products incorporate special additives in the adhesive to improve the tape's temperature resistance, chemical corrosion resistance, and other properties, making it better suited to the harsh conditions of high temperatures and chemical processing in semiconductor manufacturing.

[0004] However, the pursuit of high adhesion also presents new challenges and development needs for related technologies. One prominent issue is that increased adhesion significantly increases resistance during tape unwinding, leading to difficulties. When tape adhesion is increased, the adhesive's bonding force to the substrate becomes too strong, requiring substantial external force during unwinding. This not only causes significant inconvenience for operators, increasing operational complexity and labor intensity, but can also lead to tape stretching and deformation. Stretched and deformed tape changes in size and shape, affecting the precise attachment and removal of semiconductor components, thus impacting subsequent performance and potentially causing damage to the semiconductor component surface or incomplete removal of the protective film. Furthermore, during tape peeling, the adhesive surface comes into contact with the high-temperature platform holding the wafer. Due to limitations in the adhesive properties of existing tapes, residue is easily left during this process. This residue remains on the wafer surface or the high-temperature platform, is difficult to remove, and can contaminate semiconductor components, affecting their electrical performance and reliability, and in severe cases, even leading to product failure. Therefore, how to ensure high adhesion while achieving easy unwinding and reducing adhesive residue during tape peeling has become a pressing challenge for the development of high-adhesion peel-off tape technology. Summary of the Invention

[0005] In order to achieve easy unwinding and no residue while ensuring high adhesion, this application provides a high-cleanliness release tape for semiconductor manufacturing and its preparation process.

[0006] This application provides a high-purity film-removing tape for semiconductor manufacturing processes, employing the following technical solution: A high-cleanliness release tape for semiconductor manufacturing processes includes a PET film layer, a release layer, and an adhesive layer; the release layer is coated on one side of the PET film layer, and the adhesive layer is coated on the side of the PET film layer opposite to the release layer; the PET film layer is an opaque polyester film layer. The release layer is made from the following raw materials in parts by weight: 60-70 parts of fluorinated polyether-organosilicon graft copolymer, 15-20 parts of nano titanium dioxide, and 10-15 parts of potassium perfluorobutyl sulfonate. The adhesive layer is made from the following raw materials in parts by weight: 40-60 parts acrylate, 30-50 parts polyurethane, 10-20 parts toluene, 5-8 parts diisocyanate, 3-5 parts benzoyl peroxide, 10-20 parts rubber microparticles, 5-9 parts quaternary ammonium salt modified montmorillonite, 10-20 parts polyvinyl cinnamate, 1-3 parts photoinitiator, and 3-8 parts polyvinyl butyral.

[0007] By adopting the above technical solution, the release tape of this application, through the provision of a release layer on the back of the PET film layer, reduces the adhesive force between the adhesive layer and the PET film layer, making unwinding easier and more convenient to use. This, in turn, reduces the stretching deformation of the tape during unwinding, enhancing its adhesion strength and precision to the wafer protective film. The fluorinated polyether-organic silicone graft copolymer in the release layer has extremely low surface energy, effectively reducing the adhesion force between the adhesive layer and the PET film layer. Nano-titanium dioxide, uniformly dispersed in the release layer by potassium perfluorobutyl sulfonate, further reduces the surface energy of the release layer and forms tiny nanoscale protrusions at the microscopic level, providing physical isolation and reducing the actual contact area between the adhesive layer and the PET film layer, thereby reducing adhesive force and achieving easy unwinding.

[0008] The adhesive layer of the release tape of this application uses acrylate and polyurethane as the matrix, enabling the adhesive layer to combine the high viscosity of acrylate with the flexibility and abrasion resistance of polyurethane. The addition of rubber microparticles enhances the overall elasticity and resistance to deformation of the tape, making it less prone to deformation under tensile force. Quaternary ammonium salt modified montmorillonite, after organic quaternary ammonium salt intercalation treatment, is uniformly dispersed in the adhesive layer. Through interaction with the polymer matrix, it improves the cohesive strength and viscosity of the adhesive layer, further ensuring the tape's high viscosity. The adhesive layer of this application also contains polyvinyl cinnamate and a photoinitiator. Polyvinyl cinnamate, due to its carbon-carbon double bonds, is a highly sensitive photoresponsive monomer. When the tape is not unwound, the adhesive layer is not exposed to light, and the overall viscosity of the tape is at a relatively uniform level. Combined with the release layer, this facilitates unwinding. When the tape is torn, the adhesive layer is exposed to light. Free radicals generated by the photoinitiator initiate free radical polymerization of the photoresponsive monomers in the adhesive layer, generating new polymer segments. These new polymer segments become entangled and exert stronger intermolecular forces with other components in the adhesive layer, significantly enhancing the adhesive's own adhesion and meeting high-tack requirements. By adding polyvinyl butyral (PVB) to the adhesive layer, PVB exhibits excellent adhesion, flexibility, and optical transparency. The addition of PVB also allows it to form good compatibility with other polymer matrices (such as acrylates and polyurethanes). During the contact peeling process, the tape is subjected to tensile stress, and the adhesive surface comes into contact with the high-temperature platform of the adsorbed wafer. Temperature changes intensify the movement of the PVB molecular chains, reducing the physical entanglement points between the chains and weakening their binding forces. This reduces the interaction forces between the PVB molecular chains, macroscopically manifesting as decreased adhesion, making it easier to separate from the high-temperature platform of the adsorbed wafer and reducing residual adhesive. Meanwhile, temperature changes allow PVB to form a lubricating film at the interface between the adhesive layer and the adhered object, reducing the friction between the adhesive layer and the high-temperature platform on which the wafer is adsorbed. This makes it easier for the adhesive to detach from the surface of the high-temperature platform, thus achieving a residue-free and highly clean effect during contact peeling.

[0009] In summary, this technical solution reduces the adhesion between the adhesive layer and the PET film layer by utilizing fluorinated polyether-organic silicone graft copolymers in the release layer, thus achieving easy unwinding. The adhesive layer uses acrylate and polyurethane as the matrix, with rubber microparticles and quaternary ammonium salt modified montmorillonite to ensure high adhesion, while polyvinyl cinnamate and photoinitiators enhance the adhesion after the tape is torn. Simultaneously, the PVB in the adhesive layer, during contact peeling, experiences a decrease in its own adhesion due to temperature changes, forming a lubricating film and reducing friction. This achieves a high degree of cleanliness and residue-free contact peeling while maintaining high adhesion.

[0010] Optionally, the fluorinated polyether-organosilicon graft copolymer is prepared by the following method: A1. Mix perfluoropolyether alcohol and hydroxyl-terminated polydimethylsiloxane, add toluene and stir to form an organic solution; A2. Under inert gas protection, the organic solution is heated to 60-70℃, and then azobisisobutyronitrile is added. The reaction is carried out for 1-2 hours. After the reaction is completed, the fluorinated polyether-organosilicon graft copolymer is obtained by precipitation, filtration, washing and drying.

[0011] By employing the above technical solution, a method for preparing fluorinated polyether-organic silicone graft copolymers is provided. This involves mixing perfluoropolyether alcohol and hydroxyl-terminated polydimethylsiloxane to form an organic solution, then adding azobisisobutyronitrile (AIB) under inert gas protection to initiate the reaction, causing the two substances to undergo graft copolymerization and form a fluorinated polyether-organic silicone graft copolymer with specific structure and properties. This copolymer possesses extremely low surface energy, making it a key component in the release layer that reduces the adhesion between the adhesive layer and the PET film layer.

[0012] Optionally, the mass ratio of perfluoropolyether alcohol, hydroxyl-terminated polydimethylsiloxane and toluene in A1 is 3:(1-2):(5-7).

[0013] Optionally, the amount of azobisisobutyronitrile added in A2 is 2%-5% of the mass of the perfluoropolyether alcohol.

[0014] By adopting the above technical solution, the mass ratio of perfluoropolyether alcohol, hydroxyl-terminated polydimethylsiloxane, and toluene, as well as the amount of azobisisobutyronitrile added, were clarified. This helps to precisely control the synthesis process of fluorinated polyether-organosilicon graft copolymers, ensuring the stability and consistency of the product's performance. Appropriate raw material mass ratios and initiator dosages allow the reaction to proceed under ideal conditions, ensuring complete reaction between the perfluoropolyether alcohol and hydroxyl-terminated polydimethylsiloxane. This optimizes the molecular structure and molecular weight distribution of the graft copolymer, resulting in a good surface energy reduction effect and effectively reducing the adhesion between the adhesive layer and the PET film layer.

[0015] Optionally, the quaternary ammonium salt modified montmorillonite is prepared by the following method: B1. Mix montmorillonite with deionized water and stir to form a suspension; B2. Dissolve hexadecyltrimethylammonium bromide in anhydrous ethanol to obtain a hexadecyltrimethylammonium bromide solution; B3. Heat the suspension to 60-80℃ and stir at 200-300r / min. Then add hexadecyltrimethylammonium bromide solution to the suspension and continue stirring for 4-6 hours. After the reaction is completed, centrifuge to obtain the solid product. Wash, dry and grind the solid product to obtain quaternary ammonium salt modified montmorillonite.

[0016] By employing the above technical solution, a method for preparing quaternary ammonium salt modified montmorillonite is provided, enabling the modified montmorillonite to be better applied to adhesive layers and improve their performance. The method involves mixing montmorillonite with deionized water to form a suspension, then reacting it with a hexadecyltrimethylammonium bromide solution to insert organic quaternary ammonium salts between the montmorillonite layers, thus achieving the organic modification of montmorillonite. The modified montmorillonite can be uniformly dispersed in the adhesive layer, interacting with the polymer matrix to improve the cohesive strength and tackiness of the adhesive layer, thereby ensuring the tape has high adhesion.

[0017] Optionally, the mass ratio of montmorillonite to deionized water in B1 is 1:(10-15).

[0018] Optionally, the mass of hexadecyltrimethylammonium bromide in B2 is 10%-20% of the mass of montmorillonite, and the mass ratio of hexadecyltrimethylammonium bromide to anhydrous ethanol is 1:(8-12).

[0019] By employing the above technical solution, and using appropriate mass ratios of montmorillonite to deionized water, as well as the amounts of hexadecyltrimethylammonium bromide and its mass ratio to anhydrous ethanol, montmorillonite can be fully dispersed in water and react thoroughly with hexadecyltrimethylammonium bromide, achieving effective modification of montmorillonite. The modified montmorillonite can be uniformly dispersed in the adhesive layer, forming a good interaction with the polymer matrix and improving the bonding performance of the adhesive layer.

[0020] Optionally, the photoinitiator is either phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide or 2-hydroxy-2-methyl-1-phenylpropanone.

[0021] By employing the above technical solution, polyvinyl cinnamate, containing carbon-carbon double bonds, is a highly sensitive photoresponsive monomer. Photoinitiators such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 2-hydroxy-2-methyl-1-phenylpropanone can generate free radicals under light irradiation, initiating free radical polymerization of the photoresponsive monomers in the adhesive layer. When the tape is not unwound, the adhesive layer is not exposed to light, and its adhesion is relatively uniform, making it easy to unwound when combined with the release layer. When the tape is torn, the adhesive layer is exposed to light, and the photoinitiator initiates a polymerization reaction, generating new polymer segments. These polymer segments entangle with each other and generate stronger intermolecular forces with other components in the adhesive layer, significantly enhancing the adhesive layer's own adhesion and meeting the high-adhesion requirements.

[0022] Optionally, the adhesive layer material may further include 1-3 parts of dimethylethanolamine.

[0023] By adopting the above technical solution, dimethylethanolamine, as an accelerator, can interact with the photoinitiator to accelerate the process of the photoinitiator generating free radicals, thereby increasing the polymerization rate. When the tape is torn, dimethylethanolamine can promote the rapid generation of free radicals by the photoinitiator, thereby initiating the polymerization reaction of polyvinyl cinnamate monomers, thus improving the adhesion of the adhesive layer and meeting the requirements for high adhesion.

[0024] Secondly, this application also provides a process for preparing a high-purity peel-off tape for semiconductor manufacturing, which adopts the following technical solution: A process for preparing a high-cleanliness release tape for semiconductor manufacturing includes the following steps: S1. Preparation of release coating: Dissolve the fluorinated polyether-organosilicon graft copolymer in ethyl acetate solvent, the mass of ethyl acetate solvent being 2-3 times the mass of the fluorinated polyether-organosilicon graft copolymer. Then add nano-titanium dioxide and potassium perfluorobutyl sulfonate, and disperse ultrasonically to obtain the release coating. S2. Applying the release layer: The release layer coating is applied to one side of the PET film layer, and then dried at 90-110℃ for 1.5-2.5 min to form the release layer; S3. Preparation of adhesive layer slurry: Under light intensity of less than 1 lux, acrylate, polyurethane, toluene, diisocyanate, benzoyl peroxide, rubber microparticles, quaternary ammonium salt modified montmorillonite, polyvinyl cinnamate, photoinitiator and polyvinyl butyral are mixed, and butanone solvent is added. The mass of butanone solvent is 4-6 times the mass of acrylate. Then the mixture is stirred to obtain adhesive layer slurry. S4. Applying the adhesive layer: Under light intensity of less than 1 lux, the adhesive slurry is applied to the side of the PET film away from the release layer, and then cured at 110-140℃ for 4-7 minutes to form the adhesive layer. The coated tape is then wound up and packaged to obtain the high-cleanliness release tape for semiconductor manufacturing.

[0025] By employing the above technical solution, an adhesive layer slurry is prepared under strictly light-protected conditions with a light intensity of less than 1 lux. Multiple raw materials, including acrylate and polyurethane, are mixed, and methyl ethyl ketone (MEK) solvent is added. The specific ratio of MEK solvent mass to acrylate mass helps to uniformly disperse the raw materials in the solvent. Thorough stirring ensures that the components are integrated, forming a homogeneous and stable adhesive layer slurry. If light exposure occurs during this process, the photoinitiator absorbs light energy and is excited to generate free radicals, which will prematurely initiate the polymerization reaction of polyvinyl cinnamate, altering the adhesive layer properties. This results in the adhesive layer not meeting design expectations before use, failing to achieve the effect of enhanced adhesion upon exposure to light after tearing, and relatively weak adhesion and easy unwinding before tearing. The adhesive layer coating is also carried out under low-light conditions, and after coating, it is cured at 110-140℃ for 4-7 minutes. This temperature and time range promotes chemical reactions among the components in the adhesive layer, forming a stable adhesive structure. Meanwhile, in the above preparation method, the light-shielding operation ensures that the photoinitiator is not activated. Only after the tape is torn open and exposed to light will the photoinitiator generate free radicals to initiate the polymerization reaction of polyvinyl cinnamate, generating new polymer segments. These segments entangle with each other and generate stronger intermolecular forces with other components in the adhesive layer, thereby greatly enhancing the adhesiveness of the adhesive layer and meeting the high-adhesion requirements.

[0026] In summary, this application has the following beneficial effects: 1. This application provides a release layer on the back of the PET film layer. The fluorinated polyether-organic silicone graft copolymer has extremely low surface energy. The synergistic effect of nano-titanium dioxide and potassium perfluorobutyl sulfonate reduces the adhesion between the adhesive layer and the PET film layer, making it easy to unwind. At the same time, it reduces the stretching deformation of the tape during unwinding, and enhances the adhesion firmness and accuracy of the wafer protective film.

[0027] 2. The adhesive layer in this application uses acrylate and polyurethane as the matrix, which combines high adhesion, flexibility, and abrasion resistance. Rubber microparticles are added to enhance the resistance to deformation. It also contains polyvinyl cinnamate and a photoinitiator. When not unwound, the adhesion is relatively uniform. Combined with the release layer, it can be easily unwound. After being torn, exposure to light triggers the polymerization reaction of polyvinyl cinnamate monomers, thereby significantly enhancing the adhesion and meeting the high adhesion requirements of the tape.

[0028] 3. The polyvinyl butyral (PVB) added to the adhesive layer of this application reduces its own viscosity and forms a lubricating film due to temperature changes during contact peeling, thereby reducing the friction between the adhesive and the adhered object and making it easier for the adhesive to detach from the surface of the adhered object, achieving the effect of contact peeling without residue and high cleanliness. Attached Figure Description

[0029] Figure 1 This is the infrared spectrum of the fluorinated polyether-organosilicon graft copolymer prepared in Example 1 of this application. Detailed Implementation

[0030] The present application will be further described in detail below with reference to the embodiments.

[0031] Unless otherwise specified, all raw materials used in the preparation examples, embodiments, and comparative examples of this application are obtained from commercially available sources. The specific sources and grades of the following raw materials are provided: The black, white, and blue polyester films were all purchased from Shenzhen Anmeixin Technology Co., Ltd., with the grade PET60-75L1-bA-B and a thickness of 75±5μm.

[0032] The polyurethane was purchased from Sichuan Youborui New Materials Co., Ltd., with the grade UBRC5-30 and a solid content of 30%.

[0033] Polyvinyl cinnamate was purchased from Shanghai Zhenzhun Biotechnology Co., Ltd., with the brand name ZTR-P699170 and an average molecular weight of 100,000.

[0034] Polyvinyl butyral was purchased from Shanghai Yunhe Materials Technology Co., Ltd., with the grade BH-6 and an average molecular weight of 92,000.

[0035] The perfluoropolyether alcohol was purchased from Huihong Plastics Factory in Yuyao City. The grade was FS-1, and the average molecular weight was 3000.

[0036] The hydroxyl-terminated polydimethylsiloxane was purchased from Huangshan Qiangli Chemical Co., Ltd., with the brand name QL-200 and a purity of 99.99%.

[0037] The rubber microparticles were purchased from Dongguan Mingyu Plastic Materials Co., Ltd. as nitrile rubber powder, with an average particle size of 50 nm.

[0038] The cetyltrimethylammonium bromide was purchased from Henan Weiying Chemical Products Co., Ltd., and its effective content is greater than 99%.

[0039] The acrylate was purchased from Foshan Shangjin Chengzhan New Material Technology Co., Ltd., with the grade SGRW-3335 and a solid content of 40%.

[0040] The diisocyanate was purchased from Jinan Juxinbangshi New Material Co., Ltd., and its grade was 023.

[0041] Preparation example of fluorinated polyether-organosilicon graft copolymer Preparation Example 1 The fluorinated polyether-organosilicon graft copolymer was prepared by the following method: A1. Mix 3 kg of perfluoropolyether alcohol and 1 kg of hydroxyl-terminated polydimethylsiloxane, then add 5 kg of toluene and stir to form an organic solution. A2. Under nitrogen protection, the organic solution was heated to 60°C, and then 0.06 kg of azobisisobutyronitrile was added. The reaction was carried out for 1 hour. After the reaction was completed, the reaction solution was allowed to stand and precipitate. The solid product was then filtered to obtain the solid product. The solid product was washed three times with deionized water and then dried to constant weight in a vacuum drying oven at 60°C to obtain the fluorinated polyether-organosilicon graft copolymer.

[0042] Preparation Example 2 The fluorinated polyether-organosilicon graft copolymer was prepared by the following method: A1. Mix 3 kg of perfluorinated polyether alcohol and 1.5 kg of hydroxyl-terminated polydimethylsiloxane, then add 6 kg of toluene and stir to form an organic solution; A2. Under nitrogen protection, the organic solution was heated to 65°C, and then 0.12 kg of azobisisobutyronitrile was added. The reaction was carried out for 1.5 h. After the reaction was completed, the reaction solution was allowed to stand and precipitate. The solid product was then filtered to obtain the solid product. The solid product was washed three times with deionized water and then dried to constant weight in a vacuum drying oven at 60°C to obtain a fluorinated polyether-organosilicon graft copolymer.

[0043] Preparation Example 3 The fluorinated polyether-organosilicon graft copolymer was prepared by the following method: A1. Mix 3 kg of perfluorinated polyether alcohol and 2 kg of hydroxyl-terminated polydimethylsiloxane, then add 7 kg of toluene and stir to form an organic solution; A2. Under nitrogen protection, the organic solution was heated to 70°C, and then 0.15 kg of azobisisobutyronitrile was added. The reaction was carried out for 2 hours. After the reaction was completed, the reaction solution was allowed to stand and precipitate. The solid product was then filtered to obtain the solid product. The solid product was washed three times with deionized water and then dried to constant weight in a vacuum drying oven at 60°C to obtain the fluorinated polyether-organosilicon graft copolymer.

[0044] Preparation example of quaternary ammonium salt modified montmorillonite Preparation Example 4 Quaternary ammonium salt modified montmorillonite was prepared by the following method: B1. Mix 1 kg of montmorillonite with 10 kg of deionized water and stir at 200 r / min for 10 min to form a suspension. B2. Dissolve 0.1 kg of hexadecyltrimethylammonium bromide in 0.8 kg of anhydrous ethanol to obtain a hexadecyltrimethylammonium bromide solution; B3. The suspension was heated to 60°C and stirred at 200 r / min. Then, hexadecyltrimethylammonium bromide solution was added to the suspension and the reaction was continued for 4 h. After the reaction was completed, the solid product was obtained by centrifugation. The solid product was washed 5 times with anhydrous ethanol and deionized water alternately. Then, it was dried and ground at 60°C to obtain quaternary ammonium salt modified montmorillonite.

[0045] Preparation Example 5 Quaternary ammonium salt modified montmorillonite was prepared by the following method: B1. Mix 1 kg of montmorillonite with 12 kg of deionized water and stir at 200 r / min for 10 min to form a suspension. B2. Dissolve 0.15 kg of hexadecyltrimethylammonium bromide in 1.5 kg of anhydrous ethanol to obtain a hexadecyltrimethylammonium bromide solution; B3. The suspension was heated to 70°C and stirred at 250 r / min. Then, hexadecyltrimethylammonium bromide solution was added to the suspension and the reaction was continued for 5 h. After the reaction was completed, the solid product was obtained by centrifugation. The solid product was washed 5 times with anhydrous ethanol and deionized water alternately. Then, it was dried and ground at 60°C to obtain quaternary ammonium salt modified montmorillonite.

[0046] Preparation Example 6 Quaternary ammonium salt modified montmorillonite was prepared by the following method: B1. Mix 1 kg of montmorillonite with 15 kg of deionized water and stir at 200 r / min for 10 min to form a suspension. B2. Dissolve 0.2 kg of hexadecyltrimethylammonium bromide in 2.4 kg of anhydrous ethanol to obtain a hexadecyltrimethylammonium bromide solution; B3. The suspension was heated to 80°C and stirred at 300 r / min. Then, hexadecyltrimethylammonium bromide solution was added to the suspension and the reaction was continued for 6 h. After the reaction was completed, the solid product was obtained by centrifugation. The solid product was washed 5 times with anhydrous ethanol and deionized water alternately. Then, it was dried and ground at 60°C to obtain quaternary ammonium salt modified montmorillonite.

[0047] Example Example 1 A high-cleanliness release tape for semiconductor manufacturing processes includes a PET film layer, a release layer, and an adhesive layer; the release layer is coated on one side of the PET film layer, and the adhesive layer is coated on the side of the PET film layer opposite to the release layer; the PET film layer is a black polyester film layer.

[0048] The raw material composition and dosage of the release layer and adhesive layer are shown in Table 1. The fluorinated polyether-organosilicon graft copolymer in the release layer is the fluorinated polyether-organosilicon graft copolymer prepared in Preparation Example 1. The quaternary ammonium salt modified montmorillonite in the adhesive layer is the quaternary ammonium salt modified montmorillonite prepared in Preparation Example 4. The average particle size of the rubber particles is 50 nm. The photoinitiator is phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0049] A high-cleanliness release tape for semiconductor manufacturing processes is prepared using the following process: S1. Preparation of release coating: Dissolve the fluorinated polyether-organosilicon graft copolymer in 12 kg of ethyl acetate solvent, then add nano titanium dioxide and potassium perfluorobutyl sulfonate, and ultrasonically disperse for 30 min at an ultrasonic frequency of 60 kHz to obtain the release coating. S2. Applying the release layer: The release layer coating is applied to one side of the PET film layer, and then dried at 90°C for 2.5 minutes to form a release layer; S3. Preparation of adhesive layer slurry: Acrylate, polyurethane, toluene, diisocyanate, benzoyl peroxide, rubber microparticles, quaternary ammonium salt modified montmorillonite, polyvinyl cinnamate, photoinitiator and polyvinyl butyral are mixed in a stainless steel reactor. The light intensity in the reactor is less than 1 lux. Then, 16 kg of butanone solvent is added to the reactor and stirred at 1000 r / min for 75 min to obtain the adhesive layer slurry. S4. Applying the adhesive layer: In a dark room environment with a light intensity of less than 1 lux, apply the adhesive slurry to the side of the PET film layer away from the release layer, and then cure it at 110°C for 4 minutes to form the adhesive layer. The coated tape is then wound up and packaged to obtain the high-cleanliness release tape for semiconductor manufacturing.

[0050] Example 2 A high-cleanliness release tape for semiconductor manufacturing processes includes a PET film layer, a release layer, and an adhesive layer; the release layer is coated on one side of the PET film layer, and the adhesive layer is coated on the side of the PET film layer opposite to the release layer; the PET film layer is a white polyester film layer.

[0051] The raw material composition and dosage of the release layer and adhesive layer are shown in Table 1. The fluorinated polyether-organosilicon graft copolymer in the release layer is the fluorinated polyether-organosilicon graft copolymer prepared in Preparation Example 2. The quaternary ammonium salt modified montmorillonite in the adhesive layer is the quaternary ammonium salt modified montmorillonite prepared in Preparation Example 5. The average particle size of the rubber particles is 50 nm. The photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone.

[0052] A high-cleanliness release tape for semiconductor manufacturing processes is prepared using the following process: S1. Preparation of release coating: Dissolve the fluorinated polyether-organosilicon graft copolymer in 17 kg of ethyl acetate solvent, then add nano titanium dioxide and potassium perfluorobutyl sulfonate, and ultrasonically disperse for 45 min at an ultrasonic frequency of 50 kHz to obtain the release coating. S2. Coating the release layer: The release layer coating is applied to one side of the PET film layer, and then dried at 100°C for 2 minutes to form a release layer; S3. Preparation of adhesive layer slurry: Acrylate, polyurethane, toluene, diisocyanate, benzoyl peroxide, rubber microparticles, quaternary ammonium salt modified montmorillonite, polyvinyl cinnamate, photoinitiator and polyvinyl butyral are mixed in a stainless steel reactor. The light intensity in the reactor is less than 1 lux. Then, 25 kg of butanone solvent is added to the reactor, and the mixture is stirred at 1300 r / min for 60 min to obtain the adhesive layer slurry. S4. Applying the adhesive layer: In a dark room environment with a light intensity of less than 1 lux, apply the adhesive slurry to the side of the PET film layer away from the release layer, and then cure it at 125°C for 5 minutes to form the adhesive layer. The coated tape is then wound up and packaged to obtain the high-cleanliness release tape for semiconductor manufacturing.

[0053] Example 3 A high-cleanliness release tape for semiconductor manufacturing processes includes a PET film layer, a release layer, and an adhesive layer; the release layer is coated on one side of the PET film layer, and the adhesive layer is coated on the side of the PET film layer opposite to the release layer; the PET film layer is a blue polyester film layer.

[0054] The raw material composition and dosage of the release layer and adhesive layer are shown in Table 1. The fluorinated polyether-organosilicon graft copolymer in the release layer is the fluorinated polyether-organosilicon graft copolymer prepared in Preparation Example 3. The quaternary ammonium salt modified montmorillonite in the adhesive layer is the quaternary ammonium salt modified montmorillonite prepared in Preparation Example 6. The average particle size of the rubber particles is 50 nm. The photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone.

[0055] A high-cleanliness release tape for semiconductor manufacturing processes is prepared using the following process: S1. Preparation of release coating: Dissolve the fluorinated polyether-organosilicon graft copolymer in 24 kg of ethyl acetate solvent, then add nano titanium dioxide and potassium perfluorobutyl sulfonate, and ultrasonically disperse for 60 min at an ultrasonic frequency of 40 kHz to obtain the release coating. S2. Applying the release layer: The release layer coating is applied to one side of the PET film layer, and then dried at 110°C for 1.5 min to form a release layer; S3. Preparation of adhesive layer slurry: Acrylate, polyurethane, toluene, diisocyanate, benzoyl peroxide, rubber microparticles, quaternary ammonium salt modified montmorillonite, polyvinyl cinnamate, photoinitiator and polyvinyl butyral are mixed in a stainless steel reactor. The light intensity in the reactor is less than 1 lux. Then, 36 kg of butanone solvent is added to the reactor, and the mixture is stirred at 1500 r / min for 45 min to obtain the adhesive layer slurry. S4. Applying the adhesive layer: In a dark room environment with a light intensity of less than 1 lux, apply the adhesive slurry to the side of the PET film layer away from the release layer, and then cure it at 140°C for 7 minutes to form the adhesive layer. The coated tape is then wound up and packaged to obtain the high-cleanliness release tape for semiconductor manufacturing.

[0056] Table 1. Components and dosages (kg) of each raw material in Examples 1-3

[0057] Example 4 A high-purity release tape for semiconductor manufacturing processes differs from Example 1 in that the adhesive layer material in this example also contains 0.1 kg of dimethylethanolamine. During tape preparation, dimethylethanolamine is added to the reaction vessel along with other adhesive layer materials in step S3.

[0058] Example 5 A high-purity release tape for semiconductor manufacturing processes differs from Example 1 in that the adhesive layer material in this example also contains 0.2 kg of dimethylethanolamine. During tape preparation, dimethylethanolamine is added to the reaction vessel along with other adhesive layer materials in step S3.

[0059] Example 6 A high-purity release tape for semiconductor manufacturing processes differs from Example 1 in that the adhesive layer material in this example also contains 0.3 kg of dimethylethanolamine. During tape preparation, dimethylethanolamine is added to the reaction vessel along with other adhesive layer materials in step S3.

[0060] Comparative Example Comparative Example 1 A high-cleanliness release tape for semiconductor manufacturing processes differs from Example 5 in that the high-cleanliness release tape for semiconductor manufacturing processes in this example does not have a release layer.

[0061] Comparative Example 2 A high-cleanliness release tape for semiconductor manufacturing processes differs from Example 5 in that the release layer in this example is a polytetrafluoroethylene (PTFE) layer. To prepare the tape, a PTFE dispersion is sprayed onto a PET film layer and then dried.

[0062] Comparative Example 3 A high-purity release tape for semiconductor manufacturing processes differs from Example 5 in that nano-titanium dioxide is not added to the release layer material in this example.

[0063] Comparative Example 4 A high-purity film-removing tape for semiconductor manufacturing processes differs from Example 5 in that the adhesive layer material in this example does not contain quaternary ammonium salt modified montmorillonite.

[0064] Comparative Example 5 A high-purity peeling tape for semiconductor manufacturing processes differs from Example 5 in that the adhesive layer material in this example does not contain polyvinyl cinnamate, and the missing amount is made up with acrylate.

[0065] Comparative Example 6 A high-cleanliness release tape for semiconductor manufacturing processes differs from Example 5 in that the photoinitiator (2-hydroxy-2-methyl-1-phenylpropanone) is not added to the adhesive layer material in this example.

[0066] Comparative Example 7 A high-purity release tape for semiconductor manufacturing processes differs from Example 5 in that the adhesive layer material in this example does not contain polyvinyl butyral, and the missing amount is made up with acrylate.

[0067] Performance testing 1. Peel strength test: The peel strength of the high-cleanliness peel-off tapes prepared in Examples 1-6 and Comparative Examples 1-7 was tested according to the method specified in GB / T2792-2014 "Test method for peel strength of adhesive tape". The test results are shown in Table 2.

[0068] 2. Adhesion holding test: The adhesion holding of the high-cleanliness peel-off tapes prepared in Examples 1-6 and Comparative Examples 1-7 was tested according to the method specified in GB / T4851-2014 "Test method for adhesion holding of adhesive tapes". The test results are shown in Table 2.

[0069] 3. Unwinding strength test: The unwinding strength of the high-cleanliness peel-off tapes prepared in Examples 1-6 and Comparative Examples 1-7 was tested according to the method specified in GB / T4850-2002 "Determination of Low-Speed ​​Unwinding Strength of Pressure-Sensitive Adhesive Tapes". The test results are shown in Table 2.

[0070] 4. Removability: The test material is an alumina ceramic plate (simulating a high-temperature platform for wafer adsorption); the tape size is 12mm×110mm, the pressing conditions are 0.25MPa, the holding pressure is 10s, the wetting time is 24h, the test environment is 80℃, 50±5%RH, at a 30° angle, and the tape is stretched and removed at a removal rate of 300mm / min. The tape is recorded whether it is stretched and deformed during the removal process, and whether there is any residual adhesive on the board.

[0071] Table 2 shows the test results of Examples 1-6 and Comparative Examples 1-7.

[0072] As shown in Table 2, the peel strength of the high-cleanliness film-removing tapes in Examples 1-3 is between 35.2-35.7 N / 25 mm, the holding power is greater than 48 h, and the unwinding strength is between 0.21-0.23 N / mm. This indicates that the high-cleanliness film-removing tapes prepared in Examples 1-3 have relatively stable and similar performance. The tapes have good peel strength and holding power. By setting a release layer, the adhesion between the adhesive layer and the PET film layer is reduced, resulting in lower unwinding strength and easier unwinding.

[0073] Compared to Example 3, Examples 4-6 show a significant improvement in peel strength, reaching 43.3-43.8 N / 25 mm, while maintaining tackiness above 48 hours. Unwinding strength remains relatively stable between 0.23-0.25 N / mm. Examples 4-6, based on Example 3, incorporate dimethylethanolamine in the adhesive layer material. Dimethylethanolamine acts as an accelerator, interacting with the photoinitiator to accelerate the generation of free radicals, increasing the polymerization rate. This allows the tape to tear, and the adhesive layer's tackiness further strengthens upon light exposure, resulting in a significant increase in peel strength. Since the release layer remains unchanged, the unwinding strength remains relatively stable, and the tape continues to be easily unwound.

[0074] Comparative Example 1 exhibited a peel strength of 43.7 N / 25 mm, similar to Example 5, with a holding power greater than 48 hours and an unwinding strength as high as 1.75 N / mm. Comparative Example 3, lacking a release layer, had the adhesive layer in direct contact with the PET film layer, resulting in excessive adhesive force and a significant increase in unwinding strength, making unwinding difficult and inconvenient to use.

[0075] Comparative Example 2 exhibits a peel strength of 43.6 N / 25 mm, a holding time greater than 48 h, and an unwinding strength of 1.33 N / mm. The release layer in Comparative Example 2 uses a polytetrafluoroethylene (PTFE) layer, but its effect on reducing adhesive strength is not as good as the release layer formulation provided in this application. Although PTFE has certain low surface energy characteristics, it cannot, like the combination of fluorinated polyether-silicone graft copolymer, nano-titanium dioxide, and potassium perfluorobutyl sulfonate, synergistically reduce the adhesive strength between the adhesive layer and the PET film layer by both reducing surface energy and forming a physical isolation structure. Therefore, its unwinding strength is higher.

[0076] Comparative Example 3 exhibited a peel strength of 43.8 N / 25 mm, a holding time greater than 48 h, and an unwinding strength of 1.05 N / mm. The release layer material of Comparative Example 3 lacked the addition of nano-titanium dioxide, thus missing the synergistic effect of nano-titanium dioxide and potassium perfluorobutyl sulfonate to form a microscopic protrusion structure and further reduce surface energy. This resulted in relatively higher adhesion between the adhesive layer and the PET film layer, leading to increased unwinding strength.

[0077] Comparative Example 4 exhibited a peel strength of 12.6 N / 25 mm, a holding power of 18 h, and an unwinding strength of 0.07 N / mm. The adhesive layer material of Comparative Example 4 did not contain quaternary ammonium salt-modified montmorillonite. Quaternary ammonium salt-modified montmorillonite can improve the cohesive strength and tackiness of the adhesive layer through its interaction with the polymer matrix. Its absence leads to a significant decrease in the cohesive strength and tackiness of the adhesive layer, resulting in a significant reduction in peel strength and holding power. Simultaneously, due to the reduced tackiness of the adhesive layer, the adhesion to the PET film layer also decreases, leading to a lower unwinding strength.

[0078] Comparative Example 5 exhibited a peel strength of 23.7 N / 25 mm, a holding power of 22 h, and an unwinding strength of 0.15 N / mm. This comparative example did not contain polyvinyl cinnamate in its adhesive layer material, and the missing amount was compensated for with acrylate. Polyvinyl cinnamate undergoes a polymerization reaction under light exposure, enhancing the adhesive layer's tackiness. Its absence results in insufficient improvement in adhesive layer tackiness, decreased peel strength and holding power, and consequently, reduced tape adhesion.

[0079] Comparative Example 6 exhibited a peel strength of 25.8 N / 25 mm, a holding power of 23 h, and a unwinding strength of 0.16 N / mm. This comparative example's adhesive layer material lacked a photoinitiator, thus failing to initiate the polymerization reaction of polyvinyl cinnamate. Consequently, the adhesive layer could not effectively enhance its adhesion after light exposure, resulting in reduced peel strength and holding power. The unwinding strength also decreased due to the reduced adhesive layer tack and weakened adhesion to the PET film.

[0080] As shown in Table 2, the high-cleanliness peel-off tapes prepared in Examples 1-6 all performed excellently in the removal test. During removal, the tapes showed no stretching deformation, and no adhesive residue remained on the substrate. This indicates that the tapes prepared using this technical solution can be successfully peeled off from the simulated high-temperature platform substrate under the set test conditions without causing damage or leaving residue. Example 5, for instance, exhibited excellent overall performance, maintaining a good condition during removal. The results of no deformation and no residue verify that this technical solution can achieve clean and non-destructive tape removal in practical applications, particularly in high-temperature platforms used for wafer adsorption.

[0081] Comparative Example 7, which did not contain polyvinyl butyral in its adhesive layer material, exhibited tape stretching deformation and adhesive residue during the removability test. This directly demonstrates that polyvinyl butyral plays a crucial role in achieving a residue-free and highly clean result in this technical solution. During contact peeling, polyvinyl butyral's viscosity decreases due to temperature changes, forming a lubricating film that reduces friction with the adhered object, making it easier for the adhesive to detach from the object's surface. The absence of polyvinyl butyral leads to excessive adhesion between the tape and the substrate during removal, resulting in stretching deformation and adhesive residue, severely impacting removal effectiveness and cleanliness.

[0082] refer to Figure 1 The fluorinated polyether-organosilicon graft copolymer prepared in Preparation Example 1 was detected using a Fourier transform infrared spectroscopy (FT-IR, Nicolet 5700, Nicolet Corporation). Figure 1 The infrared spectrum of the fluorinated polyether-organosilicon graft copolymer shows that at 1113 cm⁻¹... -1 and 1264cm -1 Characteristic absorption peaks of fluorinated groups (such as -CF2-, -CF3) appeared at 1058 cm⁻¹, which are hallmark peaks of fluorinated polyether segments. -1 The characteristic absorption peak of the Si-O-Si bond appeared at 1740 cm⁻¹, which is a hallmark of organosilicon segments, indicating the presence of organosilicon components. The simultaneous appearance of the characteristic peaks of the fluorinated polyether and organosilicon is an important indication of successful grafting, suggesting that both monomers participate in the structure of the final product. -1 The presence of a characteristic absorption peak for the ester group (-COO-) at 2900 cm⁻¹ indicates that the fluorinated polyether segment and the organosilicon segment are grafted together via ester bonds, proving that the grafting reaction occurred effectively; at 2900 cm⁻¹... -1 and 3120cm -1 The presence of absorption peaks for hydrocarbon groups (such as -CH2-, -CH3, etc.) in the vicinity further confirms the existence of hydrocarbon groups in the molecular structure after grafting fluorinated polyether with organosilicon segments. Therefore, through... Figure 1It can be seen that during the preparation of the fluorinated polyether-organosilicon graft copolymer, the fluorinated polyether and organosilicon and other raw materials achieved good grafting and bonding.

[0083] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A high-cleanliness peeling tape for semiconductor manufacturing processes, characterized in that, It includes a PET film layer, a release layer, and an adhesive layer; the release layer is coated on one side of the PET film layer, and the adhesive layer is coated on the side of the PET film layer opposite to the release layer; the PET film layer is an opaque polyester film layer. The release layer is made from the following raw materials in parts by weight: 60-70 parts of fluorinated polyether-organosilicon graft copolymer, 15-20 parts of nano titanium dioxide, and 10-15 parts of potassium perfluorobutyl sulfonate. The adhesive layer is made from the following raw materials in parts by weight: 40-60 parts acrylate, 30-50 parts polyurethane, 10-20 parts toluene, 5-8 parts diisocyanate, 3-5 parts benzoyl peroxide, 10-20 parts rubber microparticles, 5-9 parts quaternary ammonium salt modified montmorillonite, 10-20 parts polyvinyl cinnamate, 1-3 parts photoinitiator, and 3-8 parts polyvinyl butyral.

2. The high-cleanliness peeling tape for semiconductor manufacturing processes according to claim 1, characterized in that: The fluorinated polyether-organosilicon graft copolymer was prepared by the following method: A1. Mix perfluoropolyether alcohol and hydroxyl-terminated polydimethylsiloxane, add toluene and stir to form an organic solution; A2. Under inert gas protection, the organic solution is heated to 60-70℃, and then azobisisobutyronitrile is added. The reaction is carried out for 1-2 hours. After the reaction is completed, the fluorinated polyether-organosilicon graft copolymer is obtained by precipitation, filtration, washing and drying.

3. The high-cleanliness peeling tape for semiconductor manufacturing processes according to claim 1, characterized in that: The mass ratio of perfluoropolyether alcohol, hydroxyl-terminated polydimethylsiloxane and toluene in A1 is 3:(1-2):(5-7).

4. The high-cleanliness peeling tape for semiconductor manufacturing according to claim 3, characterized in that: The amount of azobisisobutyronitrile added in A2 is 2%-5% of the mass of the perfluoropolyether alcohol.

5. The high-cleanliness peeling tape for semiconductor manufacturing according to claim 1, characterized in that: The quaternary ammonium salt modified montmorillonite was prepared by the following method: B1. Mix montmorillonite with deionized water and stir to form a suspension; B2. Dissolve hexadecyltrimethylammonium bromide in anhydrous ethanol to obtain a hexadecyltrimethylammonium bromide solution; B3. Heat the suspension to 60-80℃ and stir at 200-300r / min. Then add hexadecyltrimethylammonium bromide solution to the suspension and continue stirring for 4-6 hours. After the reaction is completed, centrifuge to obtain the solid product. Wash, dry and grind the solid product to obtain quaternary ammonium salt modified montmorillonite.

6. The high-cleanliness peeling tape for semiconductor manufacturing processes according to claim 5, characterized in that: The mass ratio of montmorillonite to deionized water in B1 is 1:(10-15).

7. The high-cleanliness peeling tape for semiconductor manufacturing according to claim 6, characterized in that: The mass of hexadecyltrimethylammonium bromide in B2 is 10%-20% of the mass of montmorillonite, and the mass ratio of hexadecyltrimethylammonium bromide to anhydrous ethanol is 1:(8-12).

8. The high-cleanliness peeling tape for semiconductor manufacturing according to claim 1, characterized in that: The photoinitiator is either phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide or 2-hydroxy-2-methyl-1-phenylpropanone.

9. The high-cleanliness peeling tape for semiconductor manufacturing according to claim 8, characterized in that: The adhesive layer material also includes 1-3 parts of dimethylethanolamine.

10. A process for preparing a high-purity peel-off tape for semiconductor manufacturing according to any one of claims 1-9, characterized in that, The preparation steps include the following: S1. Preparation of release coating: Dissolve the fluorinated polyether-organosilicon graft copolymer in ethyl acetate solvent, the mass of ethyl acetate solvent being 2-3 times the mass of the fluorinated polyether-organosilicon graft copolymer. Then add nano-titanium dioxide and potassium perfluorobutyl sulfonate, and disperse ultrasonically to obtain the release coating. S2. Applying the release layer: The release layer coating is applied to one side of the PET film layer, and then dried at 90-110℃ for 1.5-2.5 min to form the release layer; S3. Preparation of adhesive layer slurry: Under light intensity of less than 1 lux, acrylate, polyurethane, toluene, diisocyanate, benzoyl peroxide, rubber microparticles, quaternary ammonium salt modified montmorillonite, polyvinyl cinnamate, photoinitiator and polyvinyl butyral are mixed, and butanone solvent is added. The mass of butanone solvent is 4-6 times the mass of acrylate. Then the mixture is stirred to obtain adhesive layer slurry. S4. Applying the adhesive layer: Under light intensity of less than 1 lux, the adhesive slurry is applied to the side of the PET film away from the release layer, and then cured at 110-140℃ for 4-7 minutes to form the adhesive layer. The coated tape is then wound up and packaged to obtain the high-cleanliness release tape for semiconductor manufacturing.

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