High-stability release film for forming base plate green tape and preparation method of high-stability release film

Abstract

The invention discloses a high-stability release film for forming a substrate green tape and a preparation method of the high-stability release film. The release film comprises a base material layer, a corona layer, a high-adhesion low-expansion buffer layer, a high-modulus anti-shrinkage layer and an organic silicon release layer which are sequentially stacked, according to the invention, the low-expansion buffer layer is designed on the corona layer, the modified ZrW2O8 microspheres are added into the epoxy acrylic resin, and the negative thermal expansion property of the modified ZrW2O8 microspheres is utilized to carry out gradient buffer in the high-temperature coating process of the release film, so that the internal stress can be effectively dispersed. The invention provides the high-performance release film which can be well used for LTCC (Low Temperature Co-Fired Ceramic) raw tape casting, and the release film has the advantages of high-temperature low shrinkage, organic solvent friction resistance and stable release force, so that the stable production of the raw tape and the repeated usability can be ensured in the subsequent substrate raw tape casting process.

Description

Technical Field

[0001] This invention relates to the field of release materials, and in particular to a highly stable release film for forming green ceramic tapes on substrates and its preparation method. Background Technology

[0002] LTCC technology is a novel material technology developed by Hughes in 1982. It involves using low-temperature sintered ceramic powder to create a precisely thick and dense green ceramic tape. The desired circuit patterns are then fabricated on the green ceramic tape using processes such as laser cutting, punching, micro-hole injection, and precision conductor paste printing. Multiple passive components (such as low-capacitance capacitors, resistors, filters, impedance converters, couplers, etc.) are embedded in a multilayer ceramic substrate and then stacked together. The inner and outer electrodes can be made of metals such as silver, copper, and gold, respectively. The substrate is sintered at 900°C to create a high-density circuit that does not interfere with each other in three-dimensional space. It can also be used to create a three-dimensional circuit substrate with built-in passive components. ICs and active devices can be mounted on its surface to create passive / active integrated functional modules. This allows for further miniaturization and high density of circuits, making it particularly suitable for components used in high-frequency communication.

[0003] LTCC and HTCC technologies fabricate multilayer circuit boards by laminating and sintering green ceramic tapes. The green ceramic tape is formed by uniformly coating ceramic slurry onto a release film through a casting cutter, creating a thin film of uniform thickness and free of defects on the release surface, providing qualified material for subsequent lamination and printing processes.

[0004] Traditional release films are prone to deformation and shrinkage during high-temperature (>100℃) drying, leading to uneven thickness of the green ceramic tape and even cracking. Some release films exhibit unstable release force after high temperatures, resulting in residue and damage to the green ceramic tape during peeling. Furthermore, they suffer from poor solvent resistance; during the drying process of ceramic green casting, the surface of the release layer of the release film is corroded by organic solvents (toluene, alcohol) in the ceramic slurry, increasing subsequent peeling force and making peeling of the green ceramic tape difficult, potentially leading to tape cracking. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a high-stability release film for substrate green ceramic tape forming and a method for preparing the same, addressing the shortcomings of the prior art.

[0006] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a high-stability release film for substrate green ceramic tape forming, comprising a substrate layer, a corona layer, a high-adhesion low-expansion buffer layer, a high-modulus anti-shrinkage layer, and an organosilicon release layer stacked sequentially. The high-adhesion, low-expansion buffer layer is obtained by coating a high-adhesion, low-expansion buffer coating and then curing it. The high-adhesion, low-expansion buffer coating comprises the following raw material components by weight: 100 parts epoxy acrylate, 3-10 parts ZrW2O8 microspheres, 2-5 parts silane coupling agent, 2-5 parts first photoinitiator, and 15-35 parts first reactive diluent.

[0007] Preferably, the modified ZrW2O8 microspheres are prepared by the following method: ZrW2O8 nanopowder is dispersed in an aqueous ethanol solution, the pH is adjusted to 4-5, 1wt%-3wt% epoxy silane is added to the resulting dispersion, hydrolyzed at 50-70℃ for 2h, filtered and dried to obtain modified ZrW2O8 microspheres; The ZrW2O8 microspheres have a particle size of 20-100 nm.

[0008] Preferably, the silane coupling agent is an epoxy silane.

[0009] Preferably, the first photoinitiator is one or more of photoinitiator 184, photoinitiator 1173, or photoinitiator TPO and ITX; The first reactive diluent is one or more of IBOA or TMPTA.

[0010] Preferably, the high modulus anti-shrinkage layer is obtained by coating a high modulus anti-shrinkage coating and then curing it. The high modulus anti-shrinkage coating comprises the following raw material components by weight: 100 parts polyurethane acrylate, 3-10 parts nano clay, 2-6 parts second photoinitiator, 0.5-1.5 parts leveling agent, 10-20 parts second reactive diluent, and 300-600 parts organic solvent.

[0011] Preferably, the polyurethane acrylate is one or both of aliphatic polyurethane acrylate and aromatic polyurethane acrylate; The nano-clay is one or more of sodium-based montmorillonite and organo-montmorillonite, with a particle size ≤50nm.

[0012] Preferably, the second photoinitiator is one or more of photoinitiator 184, photoinitiator 1173, photoinitiator TPO, and photoinitiator ITX; The leveling agent is one or more of acrylic leveling agents or silicone leveling agents; The second reactive diluent is cyclic trimethylolpropane formal acrylate; The organic solvent is one or more of butanone, methyl isobutyl ketone, ethyl acetate, and propylene glycol methyl ether.

[0013] Preferably, the release layer is obtained by coating a release agent and then curing it. The release agent comprises the following raw material components by weight: 100 parts of vinyl-terminated polysiloxane, 15-30 parts of MQ silicone resin, 1.5-4 parts of methyl hydrogen silicone oil, 0.5-3 parts of anchoring agent, 2-5 parts of platinum catalyst, and 1200-2000 parts of third organic solvent.

[0014] Preferably, the molecular weight of the terminal vinyl polysiloxane is 200,000-300,000; and the molecular weight of the MQ silicone resin is 5,000-10,000. The methyl hydrogen silicone oil is one or more of the crosslinking agents SYL-OFF™ SL 7028 and SYL-OFF™ SL 7672; The anchoring agent is one or more selected from glycidyltriethoxysilane, anchoring agent SYL-OFF™ 9176, and anchoring agent SYL-OFF™ 297.

[0015] Preferably, the catalyst is a SYL-OFF™ 4000 platinum catalyst; The third organic mixed solvent is a mixed solvent composed of at least one of ketone solvents, toluene, and 120# solvent oil.

[0016] The present invention also provides a method for preparing a high-stability release film for substrate green ceramic tape molding as described above, comprising the following steps: S1. A corona layer is obtained by performing corona treatment on the coated surface of the substrate layer; S2. Apply a high-adhesion, low-expansion buffer coating onto the corona layer, and obtain a high-adhesion, low-expansion buffer layer after curing. S3. Apply a high-modulus anti-shrinkage coating onto the high-adhesion, low-expansion buffer layer, and obtain a high-modulus anti-shrinkage layer after curing. S4. Apply a release agent to the anti-shrinkage coating, and after curing, obtain a release layer, and finally obtain the high-stability release film for substrate green ceramic tape forming.

[0017] The beneficial effects of this invention are: This invention provides a high-stability release film for substrate green ceramic tape forming and its preparation method. By designing a high-adhesion, low-expansion buffer layer and a high-modulus anti-shrinkage layer below the release layer, the slippage of PET molecules is effectively controlled, and the shrinkage of PET is controlled at high temperature. This can avoid problems such as cracking of the substrate green ceramic tape due to the shrinkage of the PET base film at high temperature and high-precision thickness deviation. This invention increases the coating hardness of the release film by using a high-functionality vinyl crosslinking agent and introducing a high-hardness silicone resin in the release layer formulation. This increases the release film's resistance to solvent friction and corrosion, giving it excellent reusability. This invention designs a low-expansion buffer layer on the corona layer and adds modified ZrW2O8 microspheres to the epoxy acrylic resin. Utilizing the negative thermal expansion of the modified ZrW2O8 microspheres, a gradient buffer is provided during the high-temperature coating process of the release film, effectively dispersing internal stress. The nano-modified ZrW2O8 microsphere particles act as rigid crosslinking points, effectively preventing the slippage of PET molecular chains and effectively reducing the high-temperature shrinkage of PET. By adding epoxy silane, the epoxy groups react with the carboxyl and hydroxyl groups of PET to form covalent bonds, which can effectively hold the PET layer and modify the ZrW2O8 microspheres, thus facilitating the dispersion of nano-ZrW2O8 microspheres. A high-modulus anti-shrinkage layer is designed on the low-expansion buffer layer, and nano-clay is added to the polyurethane acrylate coating to enhance the coating modulus, thereby forming a rigid network skeleton. The nanoparticles interfere with the growth of the PET crystalline region, reducing the interfacial stress between the crystalline and amorphous regions, effectively inhibiting the slippage of PET molecular chains at high temperatures and reducing the thermal shrinkage of PET. A release layer is set on the high-modulus anti-shrinkage layer, resulting in excellent release force. By using a high-functionality vinyl crosslinking agent and introducing a high-hardness silicone resin in the release layer formulation, the coating hardness of the release film is increased, enhancing its resistance to solvent friction and corrosion, and providing a certain degree of recyclability. Detailed Implementation

[0018] The present invention will be further described in detail below with reference to embodiments, so that those skilled in the art can implement it based on the description.

[0019] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0020] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples are commercially available. For examples where specific conditions are not specified, conventional conditions or conditions recommended by the manufacturer are followed. For reagents or instruments whose manufacturers are not specified, they are all commercially available products.

[0021] The present invention provides a high-stability release film for substrate green ceramic tape forming, comprising a substrate layer, a corona layer, a high-adhesion low-expansion buffer layer, a high-modulus anti-shrinkage layer, and an organosilicon release layer stacked sequentially.

[0022] In a preferred embodiment, the substrate layer is a PET base film with a thickness of 38μm-188μm, and can be a transparent or white base film.

[0023] In a preferred embodiment, the corona layer is obtained by online corona treatment on the coating surface.

[0024] The high-adhesion, low-expansion buffer layer is obtained by coating a high-adhesion, low-expansion buffer coating and then curing it. The high-adhesion, low-expansion buffer coating includes the following raw material components by weight: 100 parts epoxy acrylate, 3-10 parts ZrW2O8 microspheres, 2-5 parts silane coupling agent, 2-5 parts first photoinitiator, and 15-35 parts first reactive diluent.

[0025] In a preferred embodiment, the epoxy acrylate resin backbone is phenolic epoxy with a viscosity of 15,000-25,000 cps.

[0026] In a preferred embodiment, the modified ZrW2O8 microspheres were prepared by the following method: ZrW2O8 nanopowder was dispersed in an aqueous ethanol solution, the pH was adjusted to 4-5, 1wt%-3wt% epoxy silane was added to the resulting dispersion, hydrolyzed at 50-70℃ for 2h, filtered and dried to obtain the modified ZrW2O8 microspheres. The ZrW2O8 microspheres have a particle size of 20-100 nm.

[0027] In a preferred embodiment, the silane coupling agent is an epoxy silane.

[0028] In a preferred embodiment, the first photoinitiator is one or more of photoinitiator 184, photoinitiator 1173, or photoinitiator TPO or ITX. In a preferred embodiment, the first reactive diluent is one or more of IBOA (isoborneol acrylate) or TMPTA (trimethylolpropane triacrylate).

[0029] In a preferred embodiment, the high modulus anti-shrinkage layer is obtained by coating a high modulus anti-shrinkage coating and then curing it. The high modulus anti-shrinkage coating comprises the following raw material components by weight: 100 parts polyurethane acrylate, 3-10 parts nano clay, 2-6 parts second photoinitiator, 0.5-1.5 parts leveling agent, 10-20 parts second reactive diluent, and 300-600 parts organic solvent.

[0030] In a preferred embodiment, the polyurethane acrylate is one or both of aliphatic polyurethane acrylate and aromatic polyurethane acrylate.

[0031] In a preferred embodiment, the nano-clay is one or more of sodium-based montmorillonite and organo-montmorillonite, with a particle size ≤50nm.

[0032] In a preferred embodiment, the second photoinitiator is one or more of photoinitiator 184, photoinitiator 1173, photoinitiator TPO, and photoinitiator ITX.

[0033] In a preferred embodiment, the leveling agent is one or more of acrylic leveling agents or silicone leveling agents; In a preferred embodiment, the second reactive diluent is a monofunctional diluent, more preferably cyclic trimethylolpropane acetal acrylate (CTFA), which has low curing shrinkage.

[0034] In a preferred embodiment, the organic solvent is one or more of butanone, methyl isobutyl ketone, ethyl acetate, and propylene glycol methyl ether.

[0035] In a preferred embodiment, the release layer is obtained by coating a release agent and then curing it. The release agent includes the following raw material components by weight: 100 parts of vinyl-terminated polysiloxane, 15-30 parts of MQ silicone resin, 1.5-4 parts of methyl hydrogen silicone oil, 0.5-3 parts of anchoring agent, 2-5 parts of platinum catalyst, and 1200-2000 parts of third organic solvent.

[0036] In a preferred embodiment, the terminal vinyl polysiloxane has a solid content of 28%-32%, a viscosity of 15,000-20,000 cps (25°C), and a molecular weight of 200,000-300,000.

[0037] In a preferred embodiment, the MQ silicone resin has a solid content of 100%, a viscosity of 500-700 cps (25°C), and a molecular weight of 5000-10000.

[0038] The methyl hydrogen silicone oil is one or more of the crosslinking agents SYL-OFF™ SL 7028 and SYL-OFF™ SL7672; The anchoring agent is selected from one or more of glycidyltriethoxysilane, anchoring agent SYL-OFF™ 9176 and anchoring agent SYL-OFF™ 297.

[0039] In a preferred embodiment, the catalyst is SYL-OFF™ 4000 catalyst, a platinum catalyst; In a preferred embodiment, the third organic mixed solvent is a mixed solvent composed of at least one of ketone solvents (such as butanone and diethyl ketone) and toluene and 120# solvent oil. Using this mixed solvent has a good coating and leveling effect.

[0040] In a preferred embodiment, the protective layer is a PFPE protective layer with a thickness of 20-50 nm.

[0041] The present invention also provides a method for preparing a high-stability release film for substrate green ceramic tape molding as described above, comprising the following steps: S1. A corona layer is obtained by performing corona treatment on the coated surface of the substrate layer; S2. Apply a high-adhesion, low-expansion buffer coating onto the corona layer, and obtain a high-adhesion, low-expansion buffer layer after curing. S3. Apply a high-modulus anti-shrinkage coating onto the high-adhesion, low-expansion buffer layer, and obtain a high-modulus anti-shrinkage layer after curing. S4. Apply a release agent to the anti-shrinkage coating, and after curing, obtain a release layer, which is the final high-stability release film used for substrate green ceramic tape forming.

[0042] The high-stability release film for substrate green ceramic tape molding provided by this invention includes: By designing a low-expansion buffer layer on the corona layer and adding modified ZrW2O8 microspheres to the epoxy acrylic resin, the negative thermal expansion of ZrW2O8 is utilized to perform gradient buffering during the high-temperature coating process of the release film, which can effectively disperse internal stress. The nano-modified ZrW2O8 microspheres act as rigid crosslinking points, effectively preventing the slippage of PET molecular chains and effectively reducing the high-temperature shrinkage of PET.

[0043] By adding epoxy silane, the epoxy groups react with the carboxyl and hydroxyl groups of PET to form covalent bonds, which can effectively bind the PET layer and also modify the nano ZrW2O8 microspheres, thus helping to disperse the nano ZrW2O8 microspheres. By designing a high-modulus anti-shrinkage layer on a low-expansion buffer layer, and adding nano-clay to the polyurethane acrylate coating to enhance the coating modulus, the coating forms a rigid network skeleton. The nanoparticles interfere with the growth of PET crystalline regions, reduce the interfacial stress between crystalline and amorphous regions, and thus effectively inhibit the slippage of PET molecular chains at high temperatures and reduce the thermal shrinkage of PET. By setting a release layer on a high-modulus anti-shrinkage layer, excellent release force can be obtained. By using a high-functionality vinyl crosslinking agent and introducing a high-hardness silicone resin in the release layer formulation, the coating hardness of the release film can be increased, thereby increasing the solvent friction resistance and solvent corrosion resistance of the release film and providing a certain degree of recyclability. This invention provides a high-performance release film that can be well used for LTCC green ceramic tape casting. It has high temperature and low shrinkage properties, resistance to organic solvent friction, and stable release force, thereby ensuring stable production of green ceramic tape and multiple reuses in the subsequent substrate green ceramic tape casting process.

[0044] The above is the general concept of the present invention. Based on this, detailed embodiments and comparative examples are provided below to further illustrate the present invention.

[0045] Example 1 A high-stability release film for substrate green ceramic tape molding comprises a substrate layer, a corona layer, a high-adhesion, low-expansion buffer layer, a high-modulus, anti-shrinkage layer, and an organosilicon release layer sequentially stacked thereon. Its preparation method includes the following steps: S1. Select a 50μm thick transparent PET base film (model 50μm transparent PET film (P51) Jiangsu Sidike New Material Technology Co., Ltd.) as the substrate layer; apply a 2KW corona discharge to the coating surface at the online corona discharge point on the substrate layer to obtain the corona layer; S2. Disperse ZrW2O8 microspheres (zirconium tungstate Shanghai Gelin Technology Co., Ltd.) in an ethanol-water solution (ethanol and water volume ratio of 60:40), adjust the pH to 5, add 2 wt% epoxy silane (KH-560 Hangzhou Jessica Chemical Co., Ltd.) to the obtained dispersion, hydrolyze at 60℃ for 2 h and then dry to obtain modified ZrW2O8 microspheres; By weight, 100 parts of epoxy acrylate (Ebecryl600 Allnex), 5 parts of modified ZrW2O8 nanospheres, 2 parts of silane coupling agent (KH-560 Hangzhou Jessica Chemical Co., Ltd.), 3 parts of the first photoinitiator (TPO BASF), 15 parts of the first reactive diluent IBOA (IBOA Jinan Boao Chemical Co., Ltd.), and 15 parts of the first reactive diluent TMPTA (TMPTA Kandis Chemical Co., Ltd.) are mixed and stirred evenly to obtain a high-adhesion, low-expansion buffer coating. A high-adhesion, low-expansion buffer coating is applied to the corona layer using a micro-grooved roller coating method, with a wet coating weight of 10 g / m². 2 UV curing was performed using a 300W / inch high-pressure mercury lamp at a curing speed of 50 m / min to obtain a high-adhesion, low-expansion buffer layer. S3. By weight, mix 100 parts of polyurethane acrylate (RJ423 Guangzhou Lihou Trading Co., Ltd.), 5 parts of organomontmorillonite (CLAYTONE40 BYK), 3 parts of second photoinitiator 184 (IGM184 Jingyi New Materials), 0.5 parts of acrylic leveling agent (BYK354 BYK Chemical), 10 parts of second reactive diluent cyclotrimethylolpropane methyl acetal acrylate (CTFA Hubei Changyao Biotechnology Co., Ltd.), 200 parts of methyl isobutyl ketone, 200 parts of propylene glycol methyl ether, and 100 parts of ethyl acetate, and stir evenly to obtain a high modulus anti-shrinkage coating. A high-modulus, anti-shrinkage coating is applied to a high-adhesion, low-expansion buffer layer using a micro-grooving roller coating method, with a wet coating weight of 10 g / m². 2 The oven temperature was set to 100℃ for thermosetting and drying, and then UV curing was performed using a 300W / inch high-pressure mercury lamp. The thermosetting and UV curing speeds were both 50 m / min, resulting in a high-modulus anti-shrinkage layer. S4. By weight, mix 100 parts of vinyl-terminated polysiloxane (SYL-OFF™ SD 7226 Dow Chemical), 20 parts of MQ silicone resin (CRA17 Wacker Chemie), 0.6 parts of anchoring agent (SYL-OFF™ 297 Dow Chemical), 1.5 parts of hydrogen-containing silicone resin (SYL-OFF™ SL 7028), 3 parts of platinum catalyst (SYL-OFF™ 4000), 380 parts of toluene solution, 600 parts of methyl ethyl ketone solution, and 300 parts of 120# solvent oil, and stir until homogeneous to obtain the release agent; Release agent is applied to the high-modulus anti-shrinkage layer using a wire-bar coating method, with a wet coating amount of 10 g / m². 2 The curing temperature is 150℃ and the curing speed is 50 m / min, and a release layer is obtained after curing; finally, a highly stable release film for substrate green ceramic tape molding is obtained.

[0046] Example 2 A high-stability release film for substrate green ceramic tape molding comprises a substrate layer, a corona layer, a high-adhesion, low-expansion buffer layer, a high-modulus, anti-shrinkage layer, and an organosilicon release layer sequentially stacked thereon. Its preparation method includes the following steps: S1. Select a 50μm thick transparent PET base film (model 50μm transparent PET film (P51) Jiangsu Sidike New Material Technology Co., Ltd.) as the substrate layer; apply a 2KW corona discharge to the coating surface at the online corona discharge point on the substrate layer to obtain the corona layer; S2. Disperse ZrW2O8 microspheres (zirconium tungstate Shanghai Gelin Technology Co., Ltd.) in an ethanol-water solution (ethanol and water volume ratio of 60:40, pH adjusted to 5, add 2 wt% epoxy silane (KH-560 Hangzhou Jessica Chemical Co., Ltd.) to the resulting dispersion, hydrolyze at 60℃ for 2 h and then dry to obtain modified ZrW2O8 microspheres; By weight, 100 parts of epoxy acrylate (Ebecryl600 Allnex), 7 parts of modified ZrW2O8 nanospheres, 2 parts of silane coupling agent (KH-560 Hangzhou Jessica Chemical Co., Ltd.), 3 parts of the first photoinitiator (TPO BASF), 15 parts of the first reactive diluent IBOA (IBOA Jinan Boao Chemical Co., Ltd.), and 15 parts of the first reactive diluent TMPTA (TMPTA Kandis Chemical Co., Ltd.) are mixed and stirred evenly to obtain a high-adhesion, low-expansion buffer coating. A high-adhesion, low-expansion buffer coating is applied to the corona layer using a micro-grooved roller coating method, with a wet coating weight of 10 g / m². 2 A high-adhesion, low-expansion buffer layer was obtained by UV curing with a 300W / inch high-pressure mercury lamp at a curing speed of 50 m / min. S3. By weight, mix 100 parts of polyurethane acrylate (RJ423 Guangzhou Lihou Trading Co., Ltd.), 5 parts of organomontmorillonite (CLAYTONE40 BYK), 3.5 parts of second photoinitiator 184 (IGM184 Jingyi New Materials), 0.5 parts of acrylic leveling agent (BYK354 BYK Chemical), 12 parts of second reactive diluent cyclotrimethylolpropane methyl acetal acrylate (CTFA Hubei Changyao Biotechnology Co., Ltd.), 200 parts of methyl isobutyl ketone, 200 parts of propylene glycol methyl ether, and 100 parts of ethyl acetate, and stir evenly to obtain a high modulus anti-shrinkage coating. A high-modulus, anti-shrinkage coating is applied to a high-adhesion, low-expansion buffer layer using a micro-grooving roller coating method, with a wet coating weight of 10 g / m². 2 The oven temperature was set to 100℃ for thermosetting drying, and then UV curing was performed using a 300W / inch high-pressure mercury lamp. The thermosetting and UV curing speeds were both 50 m / min, resulting in a high-modulus anti-shrinkage layer. S4. By weight, mix 100 parts of vinyl-terminated polysiloxane (SYL-OFF™ SD 7226 Dow Chemical), 30 parts of MQ silicone resin (CRA17 Wacker Chemie), 1 part of anchoring agent (SYL-OFF™ 297 Dow Chemical), 2.5 parts of hydrogen-containing silicone resin (SYL-OFF™ SL 7028), 3 parts of platinum catalyst (SYL-OFF™ 4000), 380 parts of toluene solution, 600 parts of methyl ethyl ketone solution, and 300 parts of 120# solvent oil, and stir until homogeneous to obtain the release agent; Release agent is applied to the high-modulus anti-shrinkage layer using a wire-bar coating method, with a wet coating amount of 10 g / m². 2 The curing temperature is 150℃ and the curing speed is 50 m / min, and a release layer is obtained after curing; finally, a highly stable release film for substrate green ceramic tape molding is obtained.

[0047] Comparative Example 1 A highly stable release film for forming green ceramic tape on a substrate comprises a substrate layer, a high-modulus anti-shrinkage layer, and an organosilicon release layer stacked sequentially. Its preparation method includes the following steps: S1. Select a 50μm thick transparent PET base film (model 50μm transparent PET film (P51) Jiangsu Sidike New Material Technology Co., Ltd.) as the substrate layer; S2. By weight, mix 100 parts of polyurethane acrylate (RJ423 Guangzhou Lihou Trading Co., Ltd.), 5 parts of organomontmorillonite (CLAYTONE40 BYK), 3 parts of second photoinitiator 184 (IGM184 Jingyi New Materials), 0.5 parts of acrylic leveling agent (BYK354 BYK Chemical), 10 parts of second reactive diluent cyclotrimethylolpropane methyl acetal acrylate (CTFA Hubei Changyao Biotechnology Co., Ltd.), 200 parts of methyl isobutyl ketone, 200 parts of propylene glycol methyl ether, and 100 parts of ethyl acetate, and stir evenly to obtain a high modulus anti-shrinkage coating. A high-modulus, anti-shrinkage coating was applied to the substrate using a micro-grooved roller coating method, with a wet coating weight of 10 g / m². 2 The oven temperature was set to 100℃ for thermosetting drying, and then UV curing was performed using a 300W / inch high-pressure mercury lamp. The thermosetting and UV curing speeds were both 50 m / min, resulting in a high-modulus anti-shrinkage layer. S3. By weight, mix 100 parts of vinyl-terminated polysiloxane (SYL-OFF™ SD 7226 Dow Chemical), 20 parts of MQ silicone resin (CRA17 Wacker Chemie), 0.6 parts of anchoring agent (SYL-OFF™ 297 Dow Chemical), 1.5 parts of hydrogen-containing silicone resin (SYL-OFF™ SL 7028), 3 parts of platinum catalyst (SYL-OFF™ 4000), 380 parts of toluene solution, 600 parts of methyl ethyl ketone solution, and 300 parts of 120# solvent oil, and stir until homogeneous to obtain the release agent; Release agent is applied to the high-modulus anti-shrinkage layer using a wire-bar coating method, with a wet coating amount of 10 g / m². 2 The curing temperature is 150℃ and the curing speed is 50 m / min, and a release layer is obtained after curing; finally, a highly stable release film for substrate green ceramic tape molding is obtained.

[0048] Comparative Example 2 A high-stability release film for forming green ceramic tape on a substrate comprises a substrate layer, a corona layer, a high-adhesion, low-expansion buffer layer, and an organosilicon release layer stacked sequentially. Its preparation method includes the following steps: S1. Select a 50μm thick transparent PET base film (model 50μm transparent PET film (P51) Jiangsu Sidike New Material Technology Co., Ltd.) as the substrate layer; apply a 2KW corona discharge to the coating surface at the online corona discharge point on the substrate layer to obtain the corona layer; S2. Disperse ZrW2O8 microspheres (zirconium tungstate Shanghai Gelin Technology Co., Ltd.) in an ethanol-water solution (ethanol and water volume ratio of 60:40), adjust the pH to 5, add 2 wt% epoxy silane (KH-560 Hangzhou Jessica Chemical Co., Ltd.) to the obtained dispersion, hydrolyze at 60℃ for 2 h and then dry to obtain modified ZrW2O8 microspheres; By weight, 100 parts of epoxy acrylate (Ebecryl600 Allnex), 5 parts of modified ZrW2O8 nanospheres, 2 parts of silane coupling agent (KH-560 Hangzhou Jessica Chemical Co., Ltd.), 3 parts of the first photoinitiator (TPO BASF), 15 parts of the first reactive diluent IBOA (IBOA Jinan Boao Chemical Co., Ltd.), and 15 parts of the first reactive diluent TMPTA (TMPTA Kandis Chemical Co., Ltd.) are mixed and stirred evenly to obtain a high-adhesion, low-expansion buffer coating. A high-adhesion, low-expansion buffer coating is applied to the corona layer using a micro-grooved roller coating method, with a wet coating weight of 10 g / m². 2 UV curing was performed using a 300W / inch high-pressure mercury lamp at a curing speed of 50 m / min to obtain a high-adhesion, low-expansion buffer layer. S3. By weight, mix 100 parts of vinyl-terminated polysiloxane (SYL-OFF™ SD 7226 Dow Chemical), 20 parts of MQ silicone resin (CRA17 Wacker Chemie), 0.6 parts of anchoring agent (SYL-OFF™ 297 Dow Chemical), 1.5 parts of hydrogen-containing silicone resin (SYL-OFF™ SL 7028), 3 parts of platinum catalyst (SYL-OFF™ 4000), 380 parts of toluene solution, 600 parts of methyl ethyl ketone solution, and 300 parts of 120# solvent oil, and stir until homogeneous to obtain the release agent; Release agent is applied to a high-adhesion, low-expansion buffer layer using a bar coating method, with a wet coating amount of 10 g / m². 2 The curing temperature is 150℃ and the curing speed is 50 m / min, and a release layer is obtained after curing; finally, a highly stable release film for substrate green ceramic tape molding is obtained.

[0049] Comparative Example 3 A high-stability release film for substrate green ceramic tape molding comprises a substrate layer, a corona layer, a high-adhesion, low-expansion buffer layer, a high-modulus, anti-shrinkage layer, and an organosilicon release layer sequentially stacked thereon. Its preparation method includes the following steps: S1. Select a 50μm thick transparent PET base film (model 50μm transparent PET film (P51) Jiangsu Sidike New Material Technology Co., Ltd.) as the substrate layer; apply a 2KW corona discharge to the coating surface at the online corona discharge point on the substrate layer to obtain the corona layer; S2. Disperse ZrW2O8 microspheres (zirconium tungstate Shanghai Gelin Technology Co., Ltd.) in an ethanol-water solution (ethanol and water volume ratio of 60:40), adjust the pH to 5, add 2 wt% epoxy silane (KH-560 Hangzhou Jessica Chemical Co., Ltd.) to the obtained dispersion, hydrolyze at 60℃ for 2 h and then dry to obtain modified ZrW2O8 microspheres; By weight, 100 parts of epoxy acrylate (Ebecryl600 Allnex), 7 parts of modified ZrW2O8 nanospheres, 2 parts of silane coupling agent (KH-560 Hangzhou Jessica Chemical Co., Ltd.), 3 parts of the first photoinitiator (TPO BASF), 15 parts of the first reactive diluent IBOA (IBOA Jinan Boao Chemical Co., Ltd.), and 15 parts of the first reactive diluent TMPTA (TMPTA Kandis Chemical Co., Ltd.) are mixed and stirred evenly to obtain a high-adhesion, low-expansion buffer coating. A high-adhesion, low-expansion buffer coating is applied to the corona layer using a micro-grooved roller coating method, with a wet coating weight of 10 g / m². 2 UV curing was performed using a 300W / inch high-pressure mercury lamp at a curing speed of 50 m / min to obtain a high-adhesion, low-expansion buffer layer. S3. By weight, mix 100 parts of polyurethane acrylate (RJ423 Guangzhou Lihou Trading Co., Ltd.), 5 parts of organomontmorillonite (CLAYTONE40 BYK), 3.5 parts of second photoinitiator 184 (IGM184 Jingyi New Materials), 0.5 parts of acrylic leveling agent (BYK354 BYK Chemical), 12 parts of second reactive diluent cyclotrimethylolpropane methyl acetal acrylate (CTFA Hubei Changyao Biotechnology Co., Ltd.), 200 parts of methyl isobutyl ketone, 200 parts of propylene glycol methyl ether, and 100 parts of ethyl acetate, and stir evenly to obtain a high modulus anti-shrinkage coating. A high-modulus, anti-shrinkage coating is applied to a high-adhesion, low-expansion buffer layer using a micro-grooving roller coating method, with a wet coating weight of 10 g / m². 2 The oven temperature was set to 100℃ for thermosetting and drying, and then UV curing was performed using a 300W / inch high-pressure mercury lamp. The thermosetting and UV curing speeds were both 50 m / min, resulting in a high-modulus anti-shrinkage layer. S4. By weight, mix 100 parts of vinyl-terminated polysiloxane (SYL-OFF™ SD 7226 Dow Chemical), 30 parts of MQ silicone resin (CRA17 Wacker Chemie), 1 part of anchoring agent (SYL-OFF™ 297 Dow Chemical), 0.5 parts of hydrogen-containing silicone resin (SYL-OFF™ SL 7028), 3 parts of platinum catalyst (SYL-OFF™ 4000), 380 parts of toluene solution, 600 parts of methyl ethyl ketone solution, and 300 parts of 120# solvent oil, and stir until homogeneous to obtain the release agent; Release agent is applied to the high-modulus anti-shrinkage layer using a wire-bar coating method, with a wet coating amount of 10 g / m². 2 The curing temperature is 150℃ and the curing speed is 50 m / min, and a release layer is obtained after curing; finally, a highly stable release film for substrate green ceramic tape molding is obtained.

[0050] The test methods or reference standards for each test item are as follows: Reference standard for release force testing: GB / T 25256 Test method for peel force and residual adhesion of optical functional films and release films; The reference standard for the release force test after toluene immersion is GB / T 25256 Test method for peel force and residual adhesion of optical functional films and release films. The conditions are that the release film is immersed in toluene solvent for 24 hours and then taken out for testing. Reference standard for hardness testing of nano-coatings: GB / T 25898-2010; Test method for the number of times release film can be recycled: simulate coating of green ceramic tape slurry on the finished release film, dry it in an oven, peel off the green ceramic tape, and repeatedly coat the green ceramic tape slurry for recycling. When peeling becomes difficult, it is determined that it can no longer be recycled, and the number of times it can be recycled is obtained. Reference standard for testing the heat recovery rate (%) of finished products: ASTM D1204; Solvent abrasion resistance test method: Prepare a mixed solvent of toluene and alcohol (1:1). Using an abrasion resistance tester, wrap a lint-free cloth around the abrasion rod of the tester and drip the mixed solvent onto the lint-free cloth (the solvent should completely soak the product). Add a 1KG weight to the abrasion rod and rub it back and forth on the release layer 40 times. If there is no obvious peeling of the release layer, it is considered OK. The test results are shown in Table 1 below: Table 1 Performance Tests of Each Embodiment and Comparative Example The test results above show that: Compared with Example 2, Example 2 uses more high-modulus anti-shrinkage layer and release layer components, which makes it exhibit lower release force and better mechanical and thermal properties.

[0051] Compared with Comparative Examples 1 and 2, Comparative Example 1 lacks a high-adhesion, low-expansion buffer layer, and Comparative Example 2 lacks a high-modulus, anti-shrinkage layer. Thus, Example 1 demonstrates that it has good release force, mechanical and thermodynamic properties, and recyclability.

[0052] Compared with Comparative Example 3, the amount of hydrogen-containing silicone resin added in Comparative Example 3 was not within the suggested limit, resulting in the coated release layer exhibiting poor release force and recyclability.

[0053] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details.

Claims

1. A high-stability release film for forming green ceramic tape on a substrate, characterized in that, It includes a substrate layer, a corona layer, a high-adhesion, low-expansion buffer layer, a high-modulus, anti-shrinkage layer, and an organosilicon release layer, which are stacked in sequence. The high-adhesion, low-expansion buffer layer is obtained by coating a high-adhesion, low-expansion buffer coating and then curing it. The high-adhesion, low-expansion buffer coating comprises the following raw material components by weight: 100 parts epoxy acrylate, 3-10 parts modified ZrW2O8 microspheres, 2-5 parts silane coupling agent, 2-5 parts first photoinitiator, and 15-35 parts first reactive diluent.

2. The high-stability release film for substrate green ceramic tape forming according to claim 1, characterized in that, Modified ZrW2O8 microspheres were prepared by the following method: ZrW2O8 nanopowder was dispersed in an aqueous ethanol solution, the pH was adjusted to 4-5, 1wt%-3wt% epoxy silane was added to the resulting dispersion, hydrolyzed at 50-70℃ for 2h, filtered and dried to obtain modified ZrW2O8 microspheres; The ZrW2O8 microspheres have a particle size of 20-100 nm.

3. The high-stability release film for substrate green ceramic tape forming according to claim 1, characterized in that, The silane coupling agent is an epoxy silane; The first photoinitiator is one or more of photoinitiator 184, photoinitiator 1173, or photoinitiator TPO and ITX; The first reactive diluent is one or more of IBOA or TMPTA.

4. The high-stability release film for substrate green ceramic tape forming according to claim 1, characterized in that, The high modulus anti-shrinkage layer is obtained by coating a high modulus anti-shrinkage coating and then curing it. The high modulus anti-shrinkage coating comprises the following raw material components by weight: 100 parts polyurethane acrylate, 3-10 parts nano clay, 2-6 parts second photoinitiator, 0.5-1.5 parts leveling agent, 10-20 parts second reactive diluent, and 300-600 parts organic solvent.

5. The high-stability release film for substrate green ceramic tape forming according to claim 4, characterized in that, The polyurethane acrylate is one or both of aliphatic polyurethane acrylate and aromatic polyurethane acrylate. The nano-clay is one or more of sodium-based montmorillonite and organo-montmorillonite, with a particle size ≤50nm.

6. The high-stability release film for substrate green ceramic tape forming according to claim 4, characterized in that, The second photoinitiator is one or more of photoinitiator 184, photoinitiator 1173, photoinitiator TPO, and photoinitiator ITX; The leveling agent is one or more of acrylic leveling agents or silicone leveling agents; The second reactive diluent is cyclic trimethylolpropane formal acrylate; The organic solvent is one or more of butanone, methyl isobutyl ketone, ethyl acetate, and propylene glycol methyl ether.

7. The high-stability release film for substrate green ceramic tape forming according to claim 1, characterized in that, The release layer is obtained by coating a release agent and then curing it. The release agent includes the following raw material components by weight: 100 parts of vinyl-terminated polysiloxane, 15-30 parts of MQ silicone resin, 1.5-4 parts of methyl hydrogen silicone oil, 0.5-3 parts of anchoring agent, 2-5 parts of platinum catalyst, and 1200-2000 parts of third organic solvent.

8. The high-stability release film for substrate green ceramic tape forming according to claim 7, characterized in that, The terminal vinyl polysiloxane has a molecular weight of 200,000-300,000; the MQ silicone resin has a molecular weight of 5,000-10,000. The methyl hydrogen silicone oil is one or more of the crosslinking agents SYL-OFF™ SL 7028 and SYL-OFF™ SL 7672; The anchoring agent is one or more selected from glycidyltriethoxysilane, anchoring agent SYL-OFF™ 9176, and anchoring agent SYL-OFF™ 297.

9. The high-stability release film for substrate green ceramic tape forming according to claim 7, characterized in that, The catalyst is SYL-OFF™ 4000 catalyst, a platinum catalyst; The third organic mixed solvent is a mixed solvent composed of at least one of ketone solvents, toluene, and 120# solvent oil.

10. A method for preparing a high-stability release film for substrate green ceramic tape forming as described in any one of claims 1-9, characterized in that, Includes the following steps: S1. A corona layer is obtained by performing corona treatment on the coated surface of the substrate layer; S2. Apply a high-adhesion, low-expansion buffer coating onto the corona layer, and obtain a high-adhesion, low-expansion buffer layer after curing. S3. Apply a high-modulus anti-shrinkage coating onto the high-adhesion, low-expansion buffer layer, and obtain a high-modulus anti-shrinkage layer after curing. S4. Apply a release agent to the anti-shrinkage coating, and after curing, obtain a release layer, and finally obtain the high-stability release film for substrate green ceramic tape forming.

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