High temperature resistant low modulus uv debonding substrate and method of making

Abstract

This invention relates to the field of semiconductor cutting UV anti-adhesion tape preparation technology, and discloses a high-temperature resistant, low-modulus UV anti-adhesion substrate and its manufacturing method. The substrate is an in-situ interface-anchored three-layer co-extrusion casting structure, composed of a corona layer, an interface bonding layer, and a low-modulus heat-resistant support layer; all three layers are made of high-melting-point thermoplastic resin. This invention, through the compounding of components of the corona layer, support layer, and interface bonding layer, ensures that each resin and additive plays a specific function. The corona layer is mainly composed of polyolefin elastomer (POP), which can reduce the substrate modulus and improve flexibility, thereby ensuring smooth film expansion during chip cutting and improving curved surface bonding ability; combined with cyclic olefin copolymer (COC), it improves heat resistance and reduces high-temperature shrinkage, allowing the substrate to maintain dimensional stability at 150°C; the addition of block polypropylene can improve toughness and impact resistance, while improving surface polarity, allowing the substrate to be directly coated with UV anti-adhesion tape without a primer.

Description

Technical Field

[0001] This invention relates to the field of semiconductor cutting UV anti-adhesion tape preparation technology, specifically to a high-temperature resistant, low-modulus UV anti-adhesion substrate and its manufacturing method. Background Technology

[0002] In semiconductor packaging and cutting, high-temperature curved surface processing of OMR optical / microelectronic components, and high-temperature protection of electronic glass, UV-resistant anti-adhesion substrates are core materials that ensure component fixation, processing accuracy, and non-destructive peeling. Currently, the most widely used high-temperature protective substrate in industry is biaxially oriented polyester film, or BOPET substrate. This type of substrate can withstand temperatures up to 180℃-220℃ and exhibits relatively good high-temperature dimensional stability, making it primarily used for high-temperature processing protection of planar electronic glass. However, BOPET substrate has an elastic modulus of no less than 4000MPa, resulting in high overall rigidity and poor flexibility. This makes it unsuitable for the film expansion process required in chip cutting and for achieving tight bonding of curved components, limiting its application scope to planar processing scenarios.

[0003] To meet the film expansion requirements of semiconductor chip dicing, the industry generally uses flexible polyolefin substrates, namely PO substrates. These substrates have low modulus and good ductility, which can complete chip film expansion and separation. However, conventional PO substrates have poor heat resistance and cannot withstand the high-temperature environment in semiconductor manufacturing processes. They are prone to shrinkage, warping, or even deformation at high temperatures. At the same time, their surface polarity is low, making it impossible to directly coat with UV anti-tack adhesives. Only transfer coating can be used, which is a complex process with high production costs. It is difficult to simultaneously meet the comprehensive requirements of high temperature resistance, low modulus, and direct coating.

[0004] Currently, the industry generally faces a technical bottleneck where high temperature resistance and low modulus are contradictory. High-temperature resistant resins typically have high modulus but insufficient flexibility, while low-modulus flexible materials have poor heat resistance and poor dimensional stability at high temperatures. In addition, multilayer substrates generally suffer from weak interlayer bonding and are prone to delamination at high temperatures, making it impossible to simultaneously meet multiple application requirements such as semiconductor cutting and film expansion, OMR high-temperature curved surface protection, and direct coating of UV adhesives.

[0005] Therefore, developing a UV-resistant substrate that combines high temperature resistance, low modulus, strong interlayer bonding, direct coating capability, and curved surface bonding capability has become an urgent technical problem to be solved in this field. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a high-temperature resistant, low-modulus UV-resistant substrate and its manufacturing method.

[0007] The specific technical solution is as follows: a high-temperature resistant, low-modulus UV-resistant substrate, wherein the substrate is an in-situ interface anchoring type three-layer co-extrusion casting structure, consisting of a corona layer, an interface bonding layer and a low-modulus heat-resistant support layer; all three layers are made of high-melting-point thermoplastic resin; the layer ratio of the corona layer: interface bonding layer: support layer is 2:1:17-4:1:15. The substrate has a heat shrinkage rate of ≤0.8% and an elastic modulus of 400-450MPa under 150℃×2h conditions. It can be directly coated with UV anti-adhesive, can be expanded into films and can be laminated to curved surfaces without delamination or peeling between layers.

[0008] As a further technical solution, the corona layer comprises the following components by mass percentage: Polyolefin elastomer POP resin 50%-70%, cyclic olefin copolymer COC resin 20%-30%, block polypropylene 10%-20%, maleic anhydride grafted COC micro powder 1%-3%, crystal form regulator 0.2%-0.6%; The POP resin has a comonomer content of ≤20%, a melting point of ≥150℃, and a melt flow rate of 2-7g / 10min (230℃, 2.16kg). The heat distortion temperature of the COC resin is ≥150℃, and the melt flow rate is 2-10g / 10min (260℃, 2.16kg). The block polypropylene has a melting point of 160℃-164℃ and a melt flow rate of 3-8g / 10min (230℃, 2.16kg). The maleic anhydride grafting rate of the maleic anhydride-grafted COC micro powder is 1.5wt%-3.0wt%.

[0009] As a further technical solution: the elastic modulus of the corona layer is 150-350 MPa; The crystal form regulator is a mixture of sorbitol nucleating agent and silane-modified hydrophobic nano-SiO2 in a mass ratio of 1:1, and the nano-SiO2 has a particle size of 10-30 nm. The sorbitol nucleating agent is selected from 1,3:2,4-di(3,4-dimethylbenzyl)sorbitol or 1,3:2,4-di(p-methylbenzyl)sorbitol.

[0010] As a further technical solution, the support layer comprises the following components by mass percentage: Low-modulus thermoplastic polyolefin elastomer 70%-90%, polymethylpentene TPX resin 10%-20%, fluorine-modified POP micro powder 0.5%-2.0%, cyclic phosphate heat shrinkage inhibitor 0.1%-0.5%; The melt flow rate of the TPX resin is 5-25 g / 10 min (260℃, 5 kg). The elastic modulus of the support layer is 400-500 MPa.

[0011] As a further technical solution, the interfacial adhesive layer is a reactive anchoring layer, comprising the following components by mass percentage: Maleic anhydride-grafted polypropylene with a melting point of 160℃: 85%-95%; Bifunctional epoxy tackifier: 3%-8%; Maleic anhydride-grafted COC micro powder: 1%-5%; The maleic anhydride grafting rate of the maleic anhydride-grafted COC micro powder is 1.5wt%-3.0wt%. The interfacial bonding layer achieves chemical anchoring bonding between the corona layer and the support layer through an in-situ covalent bond reaction of epoxy-anhydride.

[0012] As a further technical solution: the maleic anhydride-grafted polypropylene is ADMERQE500; the cyclic phosphate heat shrinkage inhibitor is sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate.

[0013] As a further technical solution: the substrate thickness is 150μm, which is suitable for semiconductor packaging and cutting, OMR high-temperature protection and high-temperature processing protection of curved components.

[0014] A method for manufacturing a high-temperature resistant, low-modulus UV-resistant, non-sticky substrate includes the following steps: (1) Preparation of maleic anhydride-grafted COC micro powder, fluorine-modified POP micro powder, crystal form regulator and cyclic phosphate heat shrinkage inhibitor; (2) The raw materials of the corona layer, the interface bonding layer and the support layer are premixed and then vacuum dried in stages: the first stage is kept at 100℃ for 2 hours, the second stage is kept at 120℃ for 3 hours, and the vacuum degree is -0.08~-0.09MPa. (3) Gradient extrusion: The extrusion temperatures of the corona layer and the support layer are 220℃, 240℃, 260℃, 275℃ and 275℃ respectively; the extrusion temperatures of the interface bonding layer are 190℃, 220℃, 245℃, 255℃ and 255℃ respectively; the temperature of the melt channel and the die head is 245-255℃. (4) Casting and three-stage heat setting: the temperature of the casting roller is 35℃, the temperature of the second cooling roller is 50℃, the temperature of the third heat setting roller is 75℃, and the traction tension is 3-8N / 200mm. (5) The corona-treated surface is corona-treated until the surface tension is 42-46 dyn, and then cooled and shaped to obtain the UV-resistant substrate.

[0015] As a further technical solution, the preparation steps of the maleic anhydride-grafted COC micro powder are as follows: Dissolve 100 parts of cyclic olefin copolymer COC micro powder in 300-500 parts of xylene and stir at 110-120℃ to dissolve; add 3-6 parts of maleic anhydride and 0.2-0.5 parts of benzoyl peroxide, and reflux at 120-125℃ for 4-6 hours under nitrogen protection; precipitate by dropping the reaction solution into acetone, filter and wash 2-3 times with acetone; vacuum dry at 80℃ for 6-8 hours, pulverize by cryogenic liquid nitrogen and pass through a 1000-1200 mesh sieve to obtain maleic anhydride grafted COC micro powder with a particle size of 5-7 μm and a maleic anhydride grafting rate of 1.5wt%-3.0wt%.

[0016] As a further technical solution, the preparation steps of the fluorine-modified POP micro powder are as follows: 100 parts of POP micro powder with a particle size of 1-5 μm were dispersed in xylene; 2-4 parts of C6-C12 fluoroalkyl acrylate, 0.5-1 parts of maleic anhydride, and 0.1-0.3 parts of benzoyl peroxide were added; the mixture was reacted at 120℃ for 4 h under nitrogen protection, precipitated with acetone, washed, dried, and then pulverized at low temperature to obtain fluorine and maleic anhydride double-grafted POE micro powder; the traction tension was 4-6 N / 200 mm.

[0017] Compared with the prior art, the present invention has the following beneficial effects: This invention achieves its goal by compounding the components of the corona layer, support layer, and interfacial adhesive layer, ensuring that each resin and additive plays a specific role. The corona layer is mainly composed of polyolefin elastomer (POP), which reduces the substrate modulus and improves flexibility, thereby ensuring smooth film expansion during chip cutting and improving the ability to bond to curved surfaces. The addition of cyclic olefin copolymer (COC) enhances heat resistance and reduces high-temperature shrinkage, allowing the substrate to maintain dimensional stability at 150°C. The addition of block polypropylene improves toughness and impact resistance, while also improving surface polarity, allowing the substrate to be directly coated with UV-resistant adhesive without a primer. Maleic anhydride-grafted COC micropowder acts as a high-temperature polarizing agent, enhancing interlayer bonding and improving heat resistance stability. A crystal structure regulator refines the material's crystalline regions, further reducing thermal shrinkage and stabilizing the corona layer modulus at 150-350 MPa. The support layer uses low-modulus thermoplastic polyolefin elastomer ABSORTOMER to provide core low modulus and high flexibility and flexural strength, keeping the overall modulus controlled at 400-500 MPa. TPX resin compounded to provide high heat resistance, low moisture absorption, low heat shrinkage, and high-temperature non-deformation properties. Fluorine-modified POP micropowder improves the strong release properties of TPX, enhances interlayer compatibility, and provides smoothness between the wafer and the expansion stage. Cyclic phosphate heat shrinkage inhibitors further stabilize dimensions and reduce high-temperature shrinkage. The support layer accounts for 75%-90% of the total thickness, serving as the mechanical framework of the substrate and determining the overall modulus and high-temperature dimensional stability. The interface adhesive layer is a compound of high-melting-point maleic anhydride-grafted polypropylene, bifunctional epoxy tackifier, and maleic anhydride-grafted COC micropowder. Chemical anchoring is achieved through an in-situ covalent bond reaction between epoxy and anhydride: the epoxy groups undergo ring-opening at high temperature and add to the MAH anhydride. The two ends of the bifunctional molecules connect to the resin components of the adhesive layer, corona layer, and support layer, forming stable molecular bridges. This specifically addresses the problems of TPX's difficulty in adhesion, weak interlayer bonding, and easy delamination at high temperatures. The adhesive layer thickness accounts for only 5%-10% of the overall thickness, not affecting the overall modulus of the substrate, yet ensuring that the layers will never delaminate. In terms of the preparation process, segmented vacuum drying removes small molecules and moisture from the raw materials, preventing film bubbles, pinholes, and appearance defects after film formation. Gradient extrusion, three-stage heat setting, and low-tension traction work synergistically to reduce internal stress in the substrate, improving high-temperature flatness and dimensional stability. Corona treatment controls the surface tension at 42-46 dyn, further ensuring that the UV-resistant adhesive can be directly coated with good adhesion.

[0018] This invention achieves a high degree of synergy between its various layers, resin formulation, reaction system, and process conditions, overcoming the technical contradiction of traditional high-temperature resistant materials where "high heat resistance inevitably leads to high modulus." Because the corona layer simultaneously achieves low modulus, high flexibility, direct coating capability, and high temperature resistance, while the support layer simultaneously achieves low modulus, high-strength skeleton, and high thermal stability, and further, a strong chemical bond is achieved through the interfacial adhesive layer, the substrate maintains heat resistance at 150℃ while its modulus is only one-tenth that of traditional BOPET, solving the industry problem of the inability to simultaneously achieve high temperature resistance and flexibility. Due to the three-layer in-situ interfacial anchoring structure, the interlayer bonding force of the substrate changes from physical adsorption to covalent bonding, preventing delamination and peeling even after high-temperature aging, thus solving the defect of easy peeling of multilayer films. Because of the optimized polarity of the corona layer and the synergy with the interfacial reaction system, the substrate can be directly coated without a primer or transfer coating, thereby reducing coating costs and simplifying the process. With the simultaneous achievement of three major characteristics—low modulus, high elongation, and low thermal shrinkage—the substrate can not only meet the needs of semiconductor chip cutting and film expansion, but also be adapted to high-temperature curved surface bonding in OMR processes, and can also be used for high-temperature processing of electronic glass, achieving versatility in multiple scenarios.

[0019] This invention achieves comprehensive performance with a heat shrinkage rate of ≤0.8% at 150℃ for 2 hours, an elastic modulus of 400-450MPa, direct UV coating capability, film expansion capability, curved surface lamination capability, and strong interlayer adhesion without delamination. It completely solves all the defects of existing technologies: overcoming the problems of high modulus and rigidity of BOPET substrates, inability to expand film, inability to laminate to curved surfaces, limited application scenarios, and inability to be directly coated; and overcoming the problems of conventional PO substrates being poorly resistant to high temperatures, experiencing large high-temperature shrinkage, only being transfer-coated, and having high costs. The solution of this invention has a clear structure, well-defined mechanism, synergistic performance, and stable process, and can simultaneously cover three major application areas: semiconductor packaging and cutting, OMR high-temperature curved surface protection, and electronic glass processing. Its comprehensive performance, process adaptability, and economy are significantly superior to existing technologies, possessing extremely high industrial application value. Detailed Implementation

[0020] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] This invention provides a high-temperature resistant, low-modulus UV-resistant adhesive substrate and its manufacturing method. The substrate is an in-situ interface-anchored three-layer co-extrusion casting structure, consisting of a corona layer, an interface bonding layer, and a low-modulus heat-resistant support layer. All three layers are made of high-melting-point thermoplastic resin, and the layer ratio of the corona layer to the interface bonding layer to the support layer is 2:1:17-4:1:15. The substrate has a heat shrinkage rate of ≤0.8% at 150℃ for 2 hours, an elastic modulus of 400-450 MPa, can be directly coated with UV-resistant adhesive, can be expanded into films, and can be laminated to curved surfaces without delamination or peeling between layers.

[0022] The corona layer of this invention comprises the following components by weight percentage: 50%-70% polyolefin elastomer (POP) resin, 20%-30% cyclic olefin copolymer (COC) resin, 10%-20% block polypropylene, 1%-3% maleic anhydride-grafted COC micropowder, and 0.2%-0.6% crystal form regulator. The POP resin has a comonomer content ≤20%, a melting point ≥150℃, and a melt flow rate of 2-7 g / 10 min (230℃, 2.16 kg). The COC resin has a heat distortion temperature ≥150℃ and a melt flow rate of 2-10 g / 10 min (260℃, 2.16 kg). The block polypropylene has a melting point of 160℃-164℃ and a melt flow rate of 3-8 g / 10 min (230℃, 2.16 kg). The maleic anhydride grafting rate of the maleic anhydride-grafted COC micropowder is 1.5 wt%-3.0 wt%. The elastic modulus of the corona layer is preferably 150-350 MPa. The crystal form regulator is a mixture of sorbitol-based nucleating agent and silane-modified hydrophobic nano-SiO2 at a mass ratio of 1:1, with the nano-SiO2 particle size being 10-30 nm. The sorbitol-based nucleating agent is selected from 1,3:2,4-di(3,4-dimethylbenzyl)sorbitol or 1,3:2,4-di(p-methylbenzyl)sorbitol.

[0023] The support layer of this invention comprises the following components by weight percentage: 70%-90% low-modulus thermoplastic polyolefin elastomer ABSORTOMER, 10%-20% polymethylpentene TPX resin, 0.5%-2.0% fluorine-modified POP micropowder, and 0.1%-0.5% cyclic phosphate heat shrinkage inhibitor. The melt flow rate of the TPX resin is 5-25 g / 10 min (260℃, 5 kg). The elastic modulus of the support layer is 400-500 MPa. The cyclic phosphate heat shrinkage inhibitor is preferably sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate.

[0024] The interfacial adhesive layer of this invention is a reactive anchoring layer, comprising the following components by weight percentage: 85%-95% maleic anhydride-grafted polypropylene with a melting point of 160℃, 3%-8% bifunctional epoxy tackifier, and 1%-5% maleic anhydride-grafted COC micropowder. The maleic anhydride grafting rate of the maleic anhydride-grafted COC micropowder is 1.5wt%-3.0wt%. The interfacial adhesive layer achieves chemical anchoring bonding between the corona layer and the support layer through an in-situ covalent bond reaction between epoxy and anhydride. The maleic anhydride-grafted polypropylene is preferably ADMERQE500.

[0025] The substrate of this invention has a thickness of 150μm and is suitable for semiconductor packaging and cutting, OMR high-temperature protection, and high-temperature processing protection of curved components.

[0026] The method for manufacturing a high-temperature resistant, low-modulus UV-resistant, non-stick substrate provided by the present invention includes the following steps: (1) Preparation of maleic anhydride-grafted COC micro powder, fluorine-modified POP micro powder, crystal form regulator and cyclic phosphate heat shrinkage inhibitor; (2) The raw materials for the corona layer, the interface bonding layer and the support layer are premixed separately and then vacuum dried in stages; (3) Gradient extrusion; (4) Casting and three-stage heat setting; (5) The corona-treated surface is subjected to corona treatment and cooled and shaped to obtain the UV-resistant substrate.

[0027] The specific steps for preparing the maleic anhydride-grafted COC micropowder are as follows: 100 parts of cyclic olefin copolymer COC micropowder are dissolved in 300-500 parts of xylene and stirred at 110-120℃; 3-6 parts of maleic anhydride and 0.2-0.5 parts of benzoyl peroxide are added, and the mixture is refluxed at 120-125℃ for 4-6 hours under nitrogen protection; the reaction solution is dropped into acetone to precipitate, filtered, and washed 2-3 times with acetone; the mixture is vacuum dried at 80℃ for 6-8 hours, pulverized with low-temperature liquid nitrogen, and passed through a 1000-1200 mesh sieve to obtain maleic anhydride-grafted COC micropowder with a particle size of 5-7 μm and a maleic anhydride grafting rate of 1.5wt%-3.0wt%.

[0028] The specific steps for preparing the fluorine-modified POP micro powder are as follows: 100 parts of POP micro powder with a particle size of 1-5 μm are dispersed in xylene; 2-4 parts of C6-C12 fluoroalkyl acrylate, 0.5-1 parts of maleic anhydride, and 0.1-0.3 parts of benzoyl peroxide are added; the mixture is reacted at 120℃ for 4 hours under nitrogen protection; after precipitation with acetone, washing, drying, and low-temperature pulverization, fluorine and maleic anhydride double-grafted POE micro powder is obtained.

[0029] The conditions for the segmented vacuum drying are as follows: the first segment is kept at 100℃ for 2 hours, the second segment is kept at 120℃ for 3 hours, and the vacuum degree is -0.08~-0.09MPa.

[0030] The conditions for gradient extrusion are as follows: the extrusion temperatures of the corona layer and the support layer are 220℃, 240℃, 260℃, 275℃, and 275℃ respectively; the extrusion temperatures of the interface bonding layer are 190℃, 220℃, 245℃, 255℃, and 255℃ respectively; and the temperatures of the melt channel and the die are 245-255℃.

[0031] The conditions for casting and three-stage heat setting are as follows: casting roller temperature 35℃, second cooling roller temperature 50℃, third heat setting roller temperature 75℃, and traction tension 3-8N / 200mm, preferably 4-6N / 200mm.

[0032] The conditions for the corona treatment are as follows: the corona-treated surface is corona-treated until the surface tension is 42-46 dyn, and then cooled and shaped to obtain the UV-resistant substrate.

[0033] This invention utilizes a three-layer in-situ interface anchoring structure, a low-modulus heat-resistant resin compound, and a reactive adhesive layer for molecular bridging. While maintaining heat resistance stability at 150℃, it reduces the elastic modulus to 400-450MPa, achieving comprehensive performance including expandable film, curved surface lamination, and direct UV-coated adhesive. The interlayer bonding is strong, and there is no delamination or peeling at high temperatures. It can be simultaneously adapted to multiple applications such as semiconductor cutting, OMR high-temperature protection, and electronic glass processing. It solves the industry problems of traditional high-temperature resistant substrates having high modulus, being unable to expand film, being unable to be laminated to curved surfaces, and conventional flexible substrates being unable to withstand high temperatures and requiring transfer coating.

[0034] To further illustrate the present invention, the following embodiments will be described in detail.

[0035] Example 1: (1) Preparation of maleic anhydride-grafted COC micro powder: 100 parts of cyclic olefin copolymer COC micro powder were dissolved in 300 parts of xylene and stirred at 110°C; 3 parts of maleic anhydride and 0.2 parts of benzoyl peroxide were added and refluxed at 120°C for 4 h under nitrogen protection; the reaction solution was dropped into acetone to precipitate, filtered and washed twice with acetone; vacuum dried at 80°C for 6 h, and after being pulverized by low temperature liquid nitrogen, it was passed through a 1000-mesh sieve to obtain maleic anhydride-grafted COC micro powder with a particle size of 5 μm and a maleic anhydride grafting rate of 1.5 wt%.

[0036] (2) Preparation of fluorine-modified POP micro powder: 100 parts of POP micro powder with a particle size of 1 μm were dispersed in xylene; 2 parts of C6-C12 fluoroalkyl acrylate, 0.5 parts of maleic anhydride and 0.1 parts of benzoyl peroxide were added; the reaction was carried out at 120℃ for 4 h under nitrogen protection, and after precipitation with acetone, washing, drying and low temperature pulverization, fluorine and maleic anhydride double-grafted POE micro powder was obtained.

[0037] (3) Preparation of corona layer raw materials: by mass percentage, 60% polyolefin elastomer POP resin, 25% cyclic olefin copolymer COC resin, 13% block polypropylene, 1.5% maleic anhydride grafted COC micro powder, and 0.5% crystal form regulator; the crystal form regulator is 1,3:2,4-di(3,4-dimethylbenzyl)sorbitol and silane-modified hydrophobic nano-SiO2 in a mass ratio of 1:1, and the nano-SiO2 particle size is 10nm.

[0038] (4) Preparation of support layer raw materials: by mass percentage, 80% low modulus thermoplastic polyolefin elastomer ABSORTOMER, 18% polymethylpentene TPX resin, 1.8% fluorine-modified POP micro powder, and 0.2% sodium 2,2'-methylene bis(4,6-di-tert-butylphenyl) phosphate.

[0039] (5) Preparation of interface adhesive layer raw materials: by mass percentage, ADMERQE500 92%, bifunctional epoxy tackifier 5%, maleic anhydride grafted COC micro powder 3%.

[0040] (6) The raw materials of the corona layer, the interface bonding layer and the support layer are premixed and then vacuum dried in stages: the first stage is kept at 100℃ for 2 hours, the second stage is kept at 120℃ for 3 hours, and the vacuum degree is -0.08MPa.

[0041] (7) Gradient extrusion: The extrusion temperatures of the corona layer and the support layer are 220℃, 240℃, 260℃, 275℃ and 275℃ respectively; the extrusion temperatures of the interface bonding layer are 190℃, 220℃, 245℃, 255℃ and 255℃ respectively; the temperature of the melt channel and the die head is 245℃.

[0042] (8) Casting and three-stage heat setting: the temperature of the casting roller is 35℃, the temperature of the second cooling roller is 50℃, the temperature of the third heat setting roller is 75℃, and the traction tension is 4N / 200mm.

[0043] (9) The corona surface is corona treated until the surface tension is 42dyn, and then cooled and shaped to obtain a UV-resistant substrate.

[0044] (10) The ratio of the substrate corona layer: interface bonding layer: support layer is 2:1:17 and the thickness is 150μm.

[0045] Example 2: (1) Preparation of maleic anhydride-grafted COC micro powder: 100 parts of cyclic olefin copolymer COC micro powder were dissolved in 400 parts of xylene and stirred at 115°C; 4.5 parts of maleic anhydride and 0.35 parts of benzoyl peroxide were added and refluxed at 122°C for 5 h under nitrogen protection; the reaction solution was dropped into acetone to precipitate, filtered and washed twice with acetone; vacuum dried at 80°C for 7 h, and after low-temperature liquid nitrogen pulverization, passed through an 1100-mesh sieve to obtain maleic anhydride-grafted COC micro powder with a particle size of 6 μm and a maleic anhydride grafting rate of 2.2 wt%.

[0046] (2) Preparation of fluorine-modified POP micro powder: 100 parts of POP micro powder with a particle size of 3 μm were dispersed in xylene; 3 parts of C6-C12 fluoroalkyl acrylate, 0.75 parts of maleic anhydride and 0.2 parts of benzoyl peroxide were added; the reaction was carried out at 120℃ for 4 h under nitrogen protection, and after precipitation with acetone, washing, drying and low temperature pulverization were carried out to obtain fluorine and maleic anhydride double-grafted POE micro powder.

[0047] (3) Preparation of corona layer raw materials: by mass percentage, 65% polyolefin elastomer POP resin, 20% cyclic olefin copolymer COC resin, 13% block polypropylene, 1.5% maleic anhydride grafted COC micro powder, and 0.5% crystal form regulator; the crystal form regulator is 1,3:2,4-di(p-methylbenzyl)sorbitol and silane-modified hydrophobic nano-SiO2 in a mass ratio of 1:1, and the nano-SiO2 particle size is 20nm.

[0048] (4) Preparation of support layer raw materials: by mass percentage, 85% of low modulus thermoplastic polyolefin elastomer ABSORTOMER, 13.8% of polymethylpentene TPX resin, 1.0% of fluorine-modified POP micro powder, and 0.2% of sodium 2,2'-methylene bis(4,6-di-tert-butylphenyl) phosphate.

[0049] (5) Preparation of interface adhesive layer raw materials: by mass percentage, ADMERQE500 92%, bifunctional epoxy tackifier 5%, maleic anhydride grafted COC micro powder 3%.

[0050] (6) The raw materials of the corona layer, the interface bonding layer and the support layer are premixed and then vacuum dried in stages: the first stage is kept at 100℃ for 2 hours, the second stage is kept at 120℃ for 3 hours, and the vacuum degree is -0.085MPa.

[0051] (7) Gradient extrusion: The extrusion temperatures of the corona layer and the support layer are 220℃, 240℃, 260℃, 275℃ and 275℃ respectively; the extrusion temperatures of the interface bonding layer are 190℃, 220℃, 245℃, 255℃ and 255℃ respectively; the temperature of the melt channel and the die head is 250℃.

[0052] (8) Casting and three-stage heat setting: the temperature of the casting roller is 35℃, the temperature of the second cooling roller is 50℃, the temperature of the third heat setting roller is 75℃, and the traction tension is 5N / 200mm.

[0053] (9) The corona-treated surface is corona-treated until the surface tension is 44dyn, and then cooled and shaped to obtain a UV-resistant substrate.

[0054] (10) The layer ratio of the substrate corona layer: interface bonding layer: support layer is 3:1:16 and the thickness is 150μm.

[0055] Example 3: (1) Preparation of maleic anhydride-grafted COC micro powder: 100 parts of cyclic olefin copolymer COC micro powder were dissolved in 500 parts of xylene and stirred at 120°C; 6 parts of maleic anhydride and 0.5 parts of benzoyl peroxide were added and refluxed at 125°C for 6 h under nitrogen protection; the reaction solution was dropped into acetone to precipitate, filtered and washed 3 times with acetone; vacuum dried at 80°C for 8 h, and after being pulverized by low temperature liquid nitrogen, it was passed through a 1200-mesh sieve to obtain maleic anhydride-grafted COC micro powder with a particle size of 7 μm and a maleic anhydride grafting rate of 3.0 wt%.

[0056] (2) Preparation of fluorine-modified POP micro powder: 100 parts of POP micro powder with a particle size of 5 μm were dispersed in xylene; 4 parts of C6-C12 fluoroalkyl acrylate, 1 part of maleic anhydride and 0.3 parts of benzoyl peroxide were added; the reaction was carried out at 120℃ for 4 h under nitrogen protection, and after precipitation with acetone, washing, drying and low temperature pulverization were carried out to obtain fluorine and maleic anhydride double-grafted POE micro powder.

[0057] (3) Preparation of corona layer raw materials: by mass percentage, 70% polyolefin elastomer POP resin, 20% cyclic olefin copolymer COC resin, 8% block polypropylene, 1.5% maleic anhydride grafted COC micro powder, and 0.5% crystal form regulator; the crystal form regulator is 1,3:2,4-di(3,4-dimethylbenzyl)sorbitol and silane-modified hydrophobic nano-SiO2 in a mass ratio of 1:1, and the nano-SiO2 particle size is 30nm.

[0058] (4) Preparation of support layer raw materials: by mass percentage, 90% low modulus thermoplastic polyolefin elastomer ABSORTOMER, 8.8% polymethylpentene TPX resin, 1.0% fluorine-modified POP micro powder, and 0.2% sodium 2,2'-methylene bis(4,6-di-tert-butylphenyl) phosphate.

[0059] (5) Preparation of interface adhesive layer raw materials: by mass percentage, ADMERQE500 92%, bifunctional epoxy tackifier 5%, maleic anhydride grafted COC micro powder 3%.

[0060] (6) The raw materials of the corona layer, the interface bonding layer and the support layer are premixed and then vacuum dried in stages: the first stage is kept at 100℃ for 2 hours, the second stage is kept at 120℃ for 3 hours, and the vacuum degree is -0.09MPa.

[0061] (7) Gradient extrusion: The extrusion temperatures of the corona layer and the support layer are 220℃, 240℃, 260℃, 275℃ and 275℃ respectively; the extrusion temperatures of the interface bonding layer are 190℃, 220℃, 245℃, 255℃ and 255℃ respectively; the temperature of the melt channel and the die head is 255℃.

[0062] (8) Casting and three-stage heat setting: the temperature of the casting roller is 35℃, the temperature of the second cooling roller is 50℃, the temperature of the third heat setting roller is 75℃, and the traction tension is 6N / 200mm.

[0063] (9) The corona-treated surface is corona-treated until the surface tension is 46dyn, and then cooled and shaped to obtain a UV-resistant substrate.

[0064] (10) The layer ratio of the substrate corona layer: interface bonding layer: support layer is 4:1:15 and the thickness is 150μm.

[0065] Comparative Example 1: Commercially available 150μm BOPET film was used, with single-sided corona treatment, and the remaining test conditions were the same as in Example 1.

[0066] Comparative Example 2: Using the same corona layer and support layer formulation as in Example 1, but without the interfacial bonding layer, the corona layer and support layer were directly co-extruded and cast, with a layer ratio of 2:18 and a thickness of 150 μm. The remaining process conditions were the same as in Example 1.

[0067] Comparative Example 3: Using the same formulations for the corona layer, interface adhesive layer, and support layer as in Example 1, the support layer is divided into two layers of the same component material, which are co-extruded and cast to form a four-layer structure with a layer ratio of 2:1:7:10 and a thickness of 150 μm. The remaining process conditions are the same as in Example 1.

[0068] Comparative Example 4: The corona layer was made of ExxonMobil 2018MA, the support layer was made of Hanwha RF402, and the process was carried out by direct co-extrusion casting. The corona surface was subjected to the same corona treatment. The layer ratio was 2:18 and the thickness was 150μm. The remaining process conditions were the same as in Example 1.

[0069] Performance testing and results analysis: Experiment 1: Elastic modulus test Test method: Performed according to GB / T1040.1-2018, using a universal testing machine, tensile rate 50 mm / min, and the average effective modulus is taken. The test results are shown in the table below: Table 1 Analysis and Summary: The elastic modulus of Examples 1-3 is 419-442 MPa, only about one-tenth that of the BOPET substrate in Comparative Example 1, exhibiting excellent flexibility and meeting the requirements for film expansion and curved surface lamination. Comparative Example 1 has an excessively high modulus and excessive rigidity, making it unsuitable for film expansion and curved surface lamination; Comparative Example 3 has an increased modulus due to its four-layer structure, resulting in decreased flexibility; Comparative Example 4 has a low modulus but poor high-temperature stability, making it unsuitable for high-temperature processes.

[0070] Experiment 2: Heat Shrinkage Rate Test Test method: Performed according to GB / T13542.2-2020. Sample size: 100mm × 10mm. The sample was sandwiched between two A4 sheets and placed in a 150℃ oven for 2 hours. After cooling to room temperature, the dimensional change rate and stickiness were measured. Test results are shown in the table below: Table 2 Analysis and Summary: Examples 1-3 all exhibited a heat shrinkage rate of ≤0.8% at 150℃ for 2 hours, demonstrating excellent high-temperature dimensional stability. Comparative Examples 1 and 4 showed significantly higher heat shrinkage rates, making them prone to deformation and warping at high temperatures. Comparative Example 2, lacking an interfacial bonding layer, and Comparative Example 3, with its four-layer structure, both resulted in increased heat shrinkage rates, failing to meet the requirements of high-temperature processes.

[0071] Test 3: Interlayer adhesion test Test method: A 180° peel strength test was conducted using Tesa 7475 adhesive tape at a peel rate of 100 mm / min. Delamination and peeling were observed. The test was then repeated after heat aging at 150℃ for 2 hours. The test results are shown in the table below: Table 3 Analysis and Summary: Examples 1-3 achieved interlayer chemical anchoring through the in-situ covalent bond reaction of epoxy-anhydride in the interfacial bonding layer, and there was no delamination or delamination even after high temperature, indicating a strong bond. Comparative Example 2 eliminated the interfacial bonding layer, and the corona layer and support layer peeled off directly; Comparative Example 3's four-layer structure led to interfacial bonding failure; Comparative Example 4 had poor material compatibility and low interlayer bonding strength, all of which failed to meet the usage requirements.

[0072] Experiment 4: Film Expansion Performance Test Test method: A chip dicing film expander (TAKATORIEFC-200A) was used with a stretching ratio of 30%. The presence of whitening, cracking, or breakage of the base film was observed, and the dicing lines were checked for uniformity. The test results are shown in the table below: Table 4 Analysis and Summary: Examples 1-3 exhibited low modulus and high flexibility, with no whitening, cracking, or breakage during film expansion, and uniform cutting patterns. Comparative Example 1 had excessive rigidity and could not expand; Comparative Example 2 experienced delamination failure during film expansion; Comparative Example 3 had poor ductility and poor film expansion effect; Comparative Example 4 had insufficient film expansion stability and could not be adapted to semiconductor cutting processes.

[0073] Experiment 5: Surface Fit Test Test method: A mirror-finish stainless steel curved fixture with a radius of 5mm (Ra≦0.5µm) was used. A UV-resistant adhesive (Changxing Chemical) with a thickness of 10µm was applied to the substrate surface using a benchtop test coating machine. The substrate was then heated at 120℃ for 30 minutes, and the presence of any peeling, bubbles, lifting, or detachment was observed. The test results are shown in the table below: Table 5 Analysis and Summary: Examples 1-3 demonstrate excellent synergy between flexibility and high-temperature stability, allowing for tight adhesion to curved surfaces without warping, bubbles, or detachment. Comparative Example 1 exhibits rigidity and cannot adhere to curved surfaces; Comparative Example 2 shows interlayer separation during adhesion; Comparative Example 3 exhibits poor adhesion; Comparative Example 4 is prone to warping at high temperatures, failing to meet the requirements for OMR high-temperature curved surface protection.

[0074] Test 6: Direct Coating Test Test method: Directly apply UV-reducing adhesive, 1020mm wide, using a 5-section drying oven at 80℃. Observe the substrate for deformation, melting and stickiness, edge shrinkage, warping, and poor adhesion. The test results are shown in the table below: Table 6 Analysis and Summary: Examples 1-3 have a reasonable corona layer polarity design and good surface wetting, allowing for direct coating of UV-resistant adhesives without deformation, stickiness, edge shrinkage, or warping, exhibiting excellent adhesion. Comparative Example 1 has a mismatched surface polarity and cannot be directly coated; Comparative Example 4 exhibits melting and stickiness at high temperatures, demonstrating extremely poor compatibility with direct coating processes.

[0075] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not describe all details exhaustively, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification.

Claims

1. A high-temperature resistant, low-modulus UV-resistant, non-stick substrate, characterized in that: The substrate is an in-situ interface anchored three-layer co-extrusion casting structure, consisting of a corona layer, an interface bonding layer, and a low-modulus heat-resistant support layer; all three layers are made of high-melting-point thermoplastic resin; the layer ratio of the corona layer: interface bonding layer: support layer is 2:1:17-4:1:

15. The substrate has a heat shrinkage rate of ≤0.8% and an elastic modulus of 400-450MPa under 150℃×2h conditions. It can be directly coated with UV anti-adhesive, can be expanded into films and can be laminated to curved surfaces without delamination or peeling between layers.

2. The UV-resistant substrate according to claim 1, characterized in that, The corona layer comprises the following components by mass percentage: Polyolefin elastomer POP resin 50%-70%, cyclic olefin copolymer COC resin 20%-30%, block polypropylene 10%-20%, maleic anhydride grafted COC micro powder 1%-3%, crystal form regulator 0.2%-0.6%; The POP resin has a comonomer content of ≤20%, a melting point of ≥150℃, and a melt flow rate of 2-7g / 10min (230℃, 2.16kg). The heat distortion temperature of the COC resin is ≥150℃, and the melt flow rate is 2-10g / 10min (260℃, 2.16kg). The block polypropylene has a melting point of 160℃-164℃ and a melt flow rate of 3-8g / 10min (230℃, 2.16kg). The maleic anhydride grafting rate of the maleic anhydride-grafted COC micro powder is 1.5wt%-3.0wt%.

3. The UV-resistant substrate according to claim 2, characterized in that: The elastic modulus of the corona layer is 150-350 MPa; The crystal form regulator is a mixture of sorbitol nucleating agent and silane-modified hydrophobic nano-SiO2 in a mass ratio of 1:1, and the nano-SiO2 has a particle size of 10-30 nm. The sorbitol nucleating agent is selected from 1,3:2,4-di(3,4-dimethylbenzyl)sorbitol or 1,3:2,4-di(p-methylbenzyl)sorbitol.

4. The UV-resistant substrate according to claim 1, characterized in that, The support layer comprises the following components by mass percentage: Low-modulus thermoplastic polyolefin elastomer 70%-90%, polymethylpentene TPX resin 10%-20%, fluorine-modified POP micro powder 0.5%-2.0%, cyclic phosphate heat shrinkage inhibitor 0.1%-0.5%; The melt flow rate of the TPX resin is 5-25 g / 10 min (260℃, 5 kg). The elastic modulus of the support layer is 400-500 MPa.

5. The UV-resistant substrate according to claim 1, characterized in that, The interfacial adhesive layer is a reactive anchoring layer, comprising the following components by mass percentage: Maleic anhydride-grafted polypropylene with a melting point of 160℃: 85%-95%; Bifunctional epoxy tackifier: 3%-8%; Maleic anhydride-grafted COC micro powder: 1%-5%; The maleic anhydride grafting rate of the maleic anhydride-grafted COC micro powder is 1.5wt%-3.0wt%. The interfacial bonding layer achieves chemical anchoring bonding between the corona layer and the support layer through an in-situ covalent bond reaction of epoxy-anhydride.

6. The UV-resistant substrate according to claim 5, characterized in that: The maleic anhydride-grafted polypropylene is ADMERQE500; the cyclic phosphate heat shrinkage inhibitor is sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate.

7. The UV-resistant substrate according to claim 1, characterized in that: The substrate has a thickness of 150μm and is suitable for semiconductor packaging and cutting, OMR high-temperature protection, and high-temperature processing protection of curved components.

8. A method for manufacturing a high-temperature resistant, low-modulus UV-resistant, non-stick substrate according to any one of claims 1-7, characterized in that, Includes the following steps: (1) Preparation of maleic anhydride-grafted COC micro powder, fluorine-modified POP micro powder, crystal form regulator and cyclic phosphate heat shrinkage inhibitor; (2) The raw materials of the corona layer, the interface bonding layer and the support layer are premixed and then vacuum dried in stages: the first stage is kept at 100℃ for 2 hours, the second stage is kept at 120℃ for 3 hours, and the vacuum degree is -0.08~-0.09MPa. (3) Gradient extrusion: The extrusion temperatures of the corona layer and the support layer are 220℃, 240℃, 260℃, 275℃ and 275℃ respectively; the extrusion temperatures of the interface bonding layer are 190℃, 220℃, 245℃, 255℃ and 255℃ respectively; the temperature of the melt channel and the die head is 245-255℃. (4) Casting and three-stage heat setting: the temperature of the casting roller is 35℃, the temperature of the second cooling roller is 50℃, the temperature of the third heat setting roller is 75℃, and the traction tension is 3-8N / 200mm. (5) The corona-treated surface is corona-treated until the surface tension is 42-46 dyn, and then cooled and shaped to obtain the UV-resistant substrate.

9. The manufacturing method according to claim 8, characterized in that, The specific steps for preparing the maleic anhydride-grafted COC micro powder are as follows: Dissolve 100 parts of cyclic olefin copolymer COC micro powder in 300-500 parts of xylene and stir at 110-120℃ to dissolve; add 3-6 parts of maleic anhydride and 0.2-0.5 parts of benzoyl peroxide, and reflux at 120-125℃ for 4-6 hours under nitrogen protection; precipitate by dropping the reaction solution into acetone, filter and wash 2-3 times with acetone; vacuum dry at 80℃ for 6-8 hours, pulverize by cryogenic liquid nitrogen and pass through a 1000-1200 mesh sieve to obtain maleic anhydride grafted COC micro powder with a particle size of 5-7 μm and a maleic anhydride grafting rate of 1.5wt%-3.0wt%.

10. The manufacturing method according to claim 8, characterized in that, The specific steps for preparing the fluorine-modified POP micro powder are as follows: 100 parts of POP micro powder with a particle size of 1-5 μm were dispersed in xylene; 2-4 parts of C6-C12 fluoroalkyl acrylate, 0.5-1 parts of maleic anhydride, and 0.1-0.3 parts of benzoyl peroxide were added; the mixture was reacted at 120℃ for 4 h under nitrogen protection, precipitated with acetone, washed, dried, and then pulverized at low temperature to obtain fluorine and maleic anhydride double-grafted POE micro powder; the traction tension was 4-6 N / 200 mm.

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