A low shrinkage and low vacuum outgassing transparent composition photoresist and a method of making a cured coating therefrom

Abstract

This invention discloses a transparent photoresist composition with low shrinkage and low vacuum degassing, comprising the following raw materials in weight percentages: 1-5% modified cage-type polysilsesquioxane (POSS), 1-5% expanded monomer, 1-5% modified acrylic resin, 1-5% epoxy resin, 1-5% thiol crosslinking agent, 1-5% initiator, 0.1-3% curing accelerator, 0.2-0.5% leveling agent, 0.1-5% silane coupling agent, 0.01-0.2% antioxidant, and 80-90% electronic-grade organic solvent. This invention also provides a method for preparing a cured coating from the transparent photoresist composition with low shrinkage and low vacuum degassing. The product of this invention not only maintains the properties of high hardness, high thermal stability, high planarization ability, high barrier properties, low moisture absorption, and low dielectric constant of the transparent composition photoresist coating, but also enables the transparent composition photoresist coating to have excellent low shrinkage and low outgassing, achieving the purpose of energy saving, emission reduction, cost reduction and efficiency improvement. The low shrinkage of the transparent composition photoresist coating also broadens the development of this material in other panel manufacturing processes such as OLED.

Description

Technical Field

[0001] This invention relates to the field of photoresists, and more particularly to a transparent composite photoresist with low shrinkage and low vacuum degassing, and a method for preparing a cured coating thereof. Background Technology

[0002] Liquid crystal displays (LCDs), as one of the most widely used display technologies, still hold more than half of the global display panel market share. Despite facing competition from newer technologies such as OLED, QD-OLED, and AMOLED, LCD technology remains dominant in large-screen TVs, monitors, advertising screens, and automotive displays due to the "trade-in" policy in China over the past two years, which has accelerated the absorption of production capacity. Rapid technological advancements and improved living standards have spurred the continuous construction and deployment of high-generation production lines, leading to fierce competition among panel manufacturers. Besides focusing on new technology innovation and high-value-added products, cost reduction, efficiency improvement, and environmental protection are also effective means for manufacturers to maintain market competitiveness.

[0003] Currently, the production of standard-sized displays does not have high requirements for the residual film rate of materials. However, in actual production, it has been found that the larger the size of the LCD substrate produced, the greater the amount of transparent photoresist required, resulting in more wasted adhesive during the wafer fabrication process. This increases the costs associated with recycling and disposal, significantly reducing economic efficiency and contradicting the current national call for low-carbon, energy-saving, and environmentally friendly practices. Furthermore, in the production of large-size panels, if the shrinkage rate of the transparent photoresist coating is too high during curing (e.g., >5% for traditional materials), it will pull on adjacent layers (such as the TFT array and color filter layer), exacerbating the unevenness between the color filter layer and the liquid crystal layer. This may further amplify the light leakage rate of the BM light-shielding layer and make it more prone to edge or local warping or even micro-cracks due to shrinkage stress, reducing product yield. Low-shrinkage coating is a core process for ensuring the yield of large-size LCDs.

[0004] Outgassing refers to the gaseous substances released by materials (such as polymers, adhesives, rubbers, or potting compounds) when heated or in a vacuum environment. Outgassing from material structures is a common phenomenon. In LCD manufacturing, the ITO sputtering process is a crucial step. In this process, the target material forms an ITO thin film on a transparent photoresist coating on the substrate, with the reaction chamber temperature reaching over 200°C. Although a significant amount of water vapor and other gaseous impurities are removed by vacuum before sputtering, a high outgassing rate in the transparent photoresist coating means more fine impurities will be released under high-temperature conditions. This can lead to the risk of "poisoning" the indium tin alloy target, reducing target utilization, and affecting the purity and etching rate of the ITO coating, ultimately impacting product yield and hindering cost savings.

[0005] Existing transparent composite photoresists and their coating processes have the following drawbacks:

[0006] 1. Existing transparent photoresist compositions typically combine epoxy polymers, acrylic resins, and other high-functionality photocurable monomers. Although the shrinkage rate of epoxy curing is lower than that of double bond curing, in practice, the volume shrinkage during polymerization and curing is significant, resulting in a coating residue rate of typically 88%-92%. A lower residue rate means a larger amount of transparent photoresist needs to be applied, leading to a greater amount of excess resist requiring post-treatment, which is detrimental to cost control. Furthermore, the stress and volumetric defects generated by shrinkage during curing exacerbate the unevenness between the color filter layer and the liquid crystal layer, accelerating coating aging and deformation, reducing overall performance, and impacting product yield.

[0007] 2. After conventional transparent photoresist curing, TGA testing shows a weight loss temperature above 300℃ for 5% TGA. However, actual outgassing tests using simulated production processes revealed significant weight loss (over 3%) above 200℃. High outgassing of the transparent photoresist coating leads to increased release of volatile organic impurities or other fine particles at high temperatures. These substances pose a risk of "poisoning" the indium tin oxide (ITO) target, affecting the purity of the ITO layer and consequently impacting product yield, increasing rework costs, and reducing target utilization, resulting in resource waste and hindering cost savings. Furthermore, in OLED processes with high rework rates, laser repair processes can cause thermal damage to the transparent photoresist coating due to laser irradiation. This outgassing may react with the organic light-emitting layer or the electrodes of the organic light-emitting layer connected to the organic light-emitting element, leading to more dark spots over time and a decline in display quality. This limits the application and development of transparent photoresist coatings in flexible display fields such as OLEDs.

[0008] 3. Existing literature: CN107075033A discloses a composition for a display sealing material. The resulting organic protective layer has a large curing shrinkage rate. After curing, stress is easily generated in the adjacent inorganic material layer in the flexible thin film encapsulation structure, leading to the cracking of the inorganic thin film layer and ultimately the failure of the thin film encapsulation structure. Patent CN103059306A discloses a high-refractive-index transparent silicone resin that improves the shrinkage of the product by introducing flexible segments. However, the introduction of too many flexible segments will reduce the mechanical properties of the material, which is not conducive to protecting chips and electronic components. CN115044244B discloses an ink composition for encapsulation with low curing shrinkage rate and its preparation method. The resulting ink composition for encapsulation with low curing shrinkage rate has high light transmittance and thermal stability, but does not involve the application of the transparent composition photoresist coating. US6680157B1 incorporates aromatic compounds into the photoresist composition to suppress or eliminate volatilization during exposure. The release of volatile byproducts can act as free radical scavengers or form stable free radicals to reduce outgassing. However, too many benzene rings in the system can lead to poor yellowing properties, affecting the contrast of the color filter substrate. CN112480851A invented a UV adhesive with reduced curing shrinkage and its preparation method, using expanded monomers in UV adhesives. This is only used in UV curing systems and does not involve any application examples of photo-thermal dual curing in the field of transparent composition photoresist planarization coatings. US20230193102A1 developed a low outgassing thermal interface material composed of thermally conductive particles dispersed in a perfluoropolyether fluid and a fluorinated surface treatment agent. Although this material can reduce mass loss under high heat conditions, some fluorinated groups (such as CF bonds) can interfere with the photochemical reaction of the photoresist, leading to light scattering and reduced pattern contrast. Moreover, some long-chain fluorinated compounds have been restricted by international conventions due to their environmental persistence and bioaccumulation, which is not conducive to environmental protection.

[0009] US20240376131A1 proposes an organometallic structure that exhibits excellent adsorption performance for volatile organic compounds (VOCs) and excellent outgassing prevention for the adsorbed VOCs. This structure is a zirconium-based organometallic structure containing fumaric acid as an organic linker. The process is complex and difficult to prepare.

[0010] In summary, existing transparent composite photoresist curing coating materials need to be improved in terms of low shrinkage and low outgassing to increase product yield, thereby achieving cost reduction and efficiency improvement, energy conservation and emission reduction, further expanding their application range in electronic products, and enhancing market competitiveness. Summary of the Invention

[0011] The purpose of this invention is to provide a transparent photoresist composition with low shrinkage and low vacuum degassing, and a method for preparing a cured coating thereof.

[0012] The innovation of this invention lies in the fact that the product of this invention not only maintains the properties of high hardness, high thermal stability, high planarization ability, high barrier properties, low moisture absorption, and low dielectric constant of the transparent composite photoresist coating, but also enables the coating to have excellent low shrinkage and low outgassing, thereby improving the yield of LCD products, achieving the goals of energy saving, emission reduction, cost reduction and efficiency improvement, and enhancing product competitiveness. The low shrinkage of the transparent composite photoresist coating also broadens the development of this material in other panel manufacturing processes such as OLED, and has broad application prospects.

[0013] To achieve the above-mentioned objectives, the technical solution of this invention is as follows:

[0014] A transparent photoresist composition with low shrinkage and low vacuum outgassing, characterized in that it comprises the following raw materials in weight percentages: 1-5% modified cage-type polysilsesquioxane (POSS), 1-5% expanded monomer, 1-5% modified acrylic resin, 1-5% epoxy resin, 1-5% thiol crosslinking agent, 1-5% initiator, 0.1-3% curing accelerator, 0.2-0.5% leveling agent, 0.1-5% silane coupling agent, 0.01-0.2% antioxidant, and 80-90% electronic grade organic solvent.

[0015] Furthermore, the modified cage-type polysilsesquioxane (POSS) has a cage-type structure with T8, and the reactive groups connected to the Si atoms at the eight vertices of the modified cage-type polysilsesquioxane (POSS) are epoxy groups, epoxycyclohexylethyl groups, or glycidyl etheroxypropyl groups, wherein the number of epoxy groups is 1 to 8.

[0016] Furthermore, the expanding monomer is a spirocyclic protocarbonate, specifically 3,9-diethyl-3',9'-dihydroxymethyl-1,5,7,11-tetraoxaspiro[5,5]undecane. 3,9-Diethylidene-2,4,8,10-tetraoxaspiro[5,5]undecane 3,9-Divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane One or more of the following.

[0017] Furthermore, the modified acrylic resin is a block polymer of polyacrylic acid, and the characteristic functional groups of the modified acrylic resin, in addition to acryloyloxy and epoxy, include at least one or more of cyclohexyl, phenyl, epoxy, cyclopentadienyl, oxetyl, dicyclopentyl, naphthyl, and glycidyl ether.

[0018] Further, the epoxy resin is at least one or a mixture of several of the following: glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresolaldehyde epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, maleimide epoxy resin, and hydantoin epoxy resin.

[0019] Further, the thiol crosslinking agent is at least one or a mixture of several of the following: trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetras(3-mercaptopropionate), 1,6-hexanedithiol, polyethylene glycol (PEG-200 / 400) dimercaptopropionate, and polycaprolactone polythiol.

[0020] Further, the initiator is at least one or a mixture of several of the following: bis(4-tert-butylphenyl)iodohexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-thionylhexafluorophosphate, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-isopropylthioxanthanone, ethyl 4-dimethylaminobenzoate, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, methyl o-benzoylbenzoate, 2,4-diethylthioxanthanone, and 1-chloro-4-propoxythioxanthanone.

[0021] Further, the curing accelerator is at least one or a mixture of several of the following: ionic curing accelerator, polycarbodiamine, tetramethyl sulfoxide, tetrabutylammonium fluoride, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, dihydrotrifluorotetrabutylammonium, triethylamine, 4-methylaminopyridine, 1,5,7-triazabicyclo[4.4.0]decene-5-ene, triphenylphosphine, n-butylphosphine, polyetheramine, benzoyl peroxide and its modified forms;

[0022] The leveling agent is at least one or a mixture of several of the following: silicone leveling agents and acrylate leveling agents;

[0023] The silane coupling agent is at least one or a mixture of several of the following: γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-glycidyl ether oxypropyltrimethoxysilane, 3-glycidyl ether oxypropyltriethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, γ-isocyanate propyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0024] The antioxidant is at least one or a mixture of several antioxidants such as aromatic amines, hindered phenols, thioethers, and phosphites;

[0025] The electronic-grade organic solvent is one or a mixture of several solvents selected from propylene glycol methyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, propylene glycol diacetate, 3-methoxybutylacetate, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, methyl N-pentyl ketone, methyl isobutyl ketone, etc.

[0026] A method for preparing a curable coating from a transparent photoresist composition with low shrinkage and low vacuum degassing is characterized by the following steps: taking modified cage-type polysilsesquioxane, expanding monomer, modified acrylic resin, epoxy resin, thiol crosslinking agent, initiator, curing accelerator, leveling agent, silane coupling agent, antioxidant, and electronic-grade organic solvent according to the formula and mixing them evenly to obtain a transparent composition, then coating, VCD, and pre-baking to obtain a film surface, and then performing dual curing of photocuring and thermocuring to obtain a cured coating.

[0027] Further, during the mixing process, 50-70% of the electronic-grade organic solvent and the remaining raw materials are first mixed evenly. During mixing, a high-speed disperser is used to disperse the mixture at 1000-1500 rpm for 20-30 minutes. Then, the remaining electronic-grade organic solvent is added and mixed evenly. During mixing, a high-speed disperser is used to disperse the mixture at 1500-2500 rpm for 5-10 minutes. During coating, the transparent composition is coated onto the substrate, and after VCD vacuum and pre-baking, the solvent evaporates to obtain the film surface. During light curing, a 2kW high-pressure mercury lamp is used for exposure at 300-1000mJ. During thermosetting, the film is baked at 80-120℃ for 1 hour.

[0028] The beneficial effects of this invention are:

[0029] 1. The expanded monomer added in this invention can improve conversion rate and precisely control volume shrinkage. Utilizing the volume expansion characteristic of the expanded monomer during ring-opening polymerization, it effectively compensates for the volume shrinkage during UV curing and epoxy curing (especially in the early stages of free radical polymerization), improving the residual film rate of the transparent composition photoresist coating. Furthermore, the spirocyclic groups of the expanded monomer are highly reactive and persistent, continuing to copolymerize with epoxy groups even after the epoxy groups have largely reacted, thereby improving the overall conversion rate of the epoxy groups, reducing unreacted monomers in the system, reducing high-temperature byproducts, and forming a higher conversion rate and a denser cross-linked network. Under these conditions, the coating experiences a high-temperature environment, significantly reducing the amount of low-molecular-weight substances that can decompose or overflow (such as unreacted monomers and small molecule fragments), thus reducing outgassing.

[0030] 2. The modified POSS in this invention possesses a three-dimensional cage-like structure. The Si-O bond energy at the core is much higher than that of the C-C bond, resulting in an extremely stable structure. Furthermore, the significant difference in electronegativity between Si and O forms polar bonds that shield the connected organic groups, greatly enhancing the material's heat resistance and oxidation resistance. In addition, its unique cage-like structure and low polarity endow the material with an ultra-low dielectric constant, making it suitable for high-frequency electronic applications. During the curing process, the epoxy groups at the POSS terminals undergo ring-opening cross-linking, forming a rigid three-dimensional structure that further increases the overall cross-linking density, creating a denser three-dimensional network. This effectively reduces the free volume of the molecular chains, decreases residual stress, and also improves the coating's barrier properties against moisture or other gases.

[0031] 3. The curing process of this invention utilizes a "click chemistry" reaction between thiols and ethoxyls and epoxy groups. The double bonds of thiols and acrylic resins can undergo rapid, efficient, and selective addition reactions under mild conditions, with almost no small molecule byproducts generated, conforming to the principles of green chemistry and significantly reducing small molecule substances that may cause outgassing at the source. During the thermosetting process, excess thiols after photocuring undergo a "click reaction" with the epoxy groups of POSS or acrylic resin, as well as the spirocyclic rings of the expanding monomers, under the action of a catalyst, forming a dense three-dimensional cross-linked network and reducing outgassing.

[0032] 4. This invention employs a dual photothermal curing process, triggering different reactions step-by-step to construct an interpenetrating dense network. In the UV curing stage, ultraviolet light rapidly initiates the thiol-olefin click reaction, achieving initial crosslinking and localization. In the thermocuring stage, the heating process triggers excess thiol crosslinking agent to initiate the ring-opening polymerization of epoxy groups and spirocyclic compounds. The volume expansion caused by the ring-opening of the expanding monomers in the thermocuring stage effectively compensates for the volume shrinkage generated in the UV curing stage, achieving extremely low net volume shrinkage. The different chemical crosslinking structures formed by the two curing methods interpenetrate and intertwine, forming an extremely dense and low-branched three-dimensional interpenetrating network. Combined with the barrier effect of POSS, this minimizes the decomposition and spillage of small molecules at high temperatures, achieving low outgassing and thus reducing costs, increasing efficiency, and promoting environmental friendliness. Detailed Implementation

[0033] The technical solutions in the embodiments of the present invention will be clearly and completely described below.

[0034] Example 1: A transparent photoresist composition with low shrinkage and low vacuum outgassing, comprising the following raw materials in weight percentages: 1% modified cage-type polysilsesquioxane (POSS), 1% expanded monomer, 1% modified acrylic resin, 5% epoxy resin, 2% thiol crosslinking agent, 1.3% initiator, 3% curing accelerator, 0.5% leveling agent, 5% silane coupling agent, 0.2% antioxidant, and 80% electronic grade organic solvent.

[0035] Modified cage-type polysilsesquioxane (POSS) has a cage-type structure with T8. The reactive groups attached to the Si atoms at the eight vertices of modified cage-type polysilsesquioxane (POSS) are epoxy groups, with one epoxy group attached to each.

[0036] The expanding monomer is a spirocyclic protocarbonate, specifically 3,9-diethyl-3',9'-dihydroxymethyl-1,5,7,11-tetraoxaspiro[5,5]undecane.

[0037] Modified acrylic resin is a block polymer of polyacrylic acid. In addition to acryloyloxy and epoxy groups, the characteristic functional groups of modified acrylic resin also include cyclohexyl.

[0038] The epoxy resin is a glycidyl ether epoxy resin.

[0039] The thiol crosslinking agent is trimethylolpropane tris(3-mercaptopropionate).

[0040] The initiator is 2-isopropylthioxanthrone.

[0041] The curing accelerator is an ionic curing accelerator;

[0042] The leveling agent is an organosilicon-based leveling agent;

[0043] The silane coupling agent is γ-aminopropyltrimethoxysilane;

[0044] The antioxidants are aromatic amines;

[0045] The electronic-grade organic solvent is propylene glycol methyl ether.

[0046] Example 2: A transparent photoresist composition with low shrinkage and low vacuum outgassing, comprising the following raw materials in weight percentages: 5% modified cage-type polysilsesquioxane (POSS), 5% expanded monomer, 2% modified acrylic resin, 1% epoxy resin, 1% thiol crosslinking agent, 1% initiator, 0.2% curing accelerator, 0.4% leveling agent, 1% silane coupling agent, 0.03% antioxidant, and 83.37% electronic grade organic solvent.

[0047] Modified cage-type polysilsesquioxane (POSS) has a cage-type structure with T8. The reactive groups attached to the Si atoms at the eight vertices of the modified cage-type polysilsesquioxane (POSS) are epoxy groups and epoxycyclohexylethyl groups, with four epoxy groups in total.

[0048] The expanding monomer is a spirocyclic protocarbonate, specifically 3,9-diethylidene-2,4,8,10-tetraoxaspiro[5,5]undecane.

[0049] Modified acrylic resin is a block polymer of polyacrylic acid. In addition to acryloyloxy and epoxy groups, the characteristic functional groups of modified acrylic resin also include phenyl groups.

[0050] The epoxy resin is a glycidyl ester epoxy resin.

[0051] The thiol crosslinking agent is pentaerythritol tetra(3-mercaptopropionate).

[0052] The initiator is 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone.

[0053] The curing accelerator is polycarbodiamine;

[0054] The leveling agent is an acrylic leveling agent;

[0055] The silane coupling agent is N-β-aminoethyl-γ-aminopropyltrimethoxysilane;

[0056] The antioxidant is a hindered phenol;

[0057] The electronic-grade organic solvent is propylene glycol methyl ether acetate.

[0058] Example 3: A transparent photoresist composition with low shrinkage and low vacuum outgassing, comprising the following raw materials in weight percentages: 3% modified cage-type polysilsesquioxane (POSS), 2% expanded monomer, 2% modified acrylic resin, 2% epoxy resin, 5% thiol crosslinking agent, 5% initiator, 0.5% curing accelerator, 0.3% leveling agent, 0.15% silane coupling agent, 0.05% antioxidant, and 80% electronic grade organic solvent.

[0059] Modified cage-type polysilsesquioxane (POSS) has a cage-type structure with T8. The reactive groups attached to the Si atoms at the eight vertices of the modified cage-type polysilsesquioxane (POSS) are epoxy groups and glycidyl etheroxypropyl groups, with eight epoxy groups in total.

[0060] The expanding monomer is a spirocyclic protocarbonate, specifically 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0061] Modified acrylic resin is a block polymer of polyacrylic acid. In addition to acryloyloxy and epoxy groups, the characteristic functional groups of modified acrylic resin also include epoxy groups.

[0062] The epoxy resin is a glycidylamine epoxy resin.

[0063] The thiol crosslinking agent is 1,6-hexanedithiol.

[0064] The initiator is (2,4,6-trimethylbenzoyl)diphenylphosphine oxide.

[0065] The curing accelerator is tetramethyl sulfoxide;

[0066] The leveling agent is an organosilicon-based leveling agent;

[0067] The silane coupling agent is N-phenyl-γ-aminopropyltrimethoxysilane;

[0068] The antioxidants are sulfides;

[0069] The electronic-grade organic solvent is diethylene glycol methyl ethyl ether.

[0070] Example 4: A transparent photoresist composition with low shrinkage and low vacuum outgassing, comprising the following raw materials in weight percentages: 1% modified cage-type polysilsesquioxane (POSS), 1% expanded monomer, 4.59% modified acrylic resin, 1% epoxy resin, 1% alcohol crosslinking agent, 1% initiator, 0.1% curing accelerator, 0.2% leveling agent, 0.1% silane coupling agent, 0.01% antioxidant, and 90% electronic grade organic solvent.

[0071] Modified cage-type polysilsesquioxane (POSS) has a cage-type structure with T8. The reactive groups attached to the Si atoms at the eight vertices of the modified cage-type polysilsesquioxane (POSS) are epoxy groups and epoxycyclohexylethyl groups, with three epoxy groups.

[0072] The expanding monomer is a spirocyclic protocarbonate, specifically 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0073] Modified acrylic resin is a block polymer of polyacrylic acid. In addition to acryloyloxy and epoxy groups, the characteristic functional groups of modified acrylic resin also include cyclopentadienyl groups.

[0074] The epoxy resin is bisphenol A epoxy resin.

[0075] The thiol crosslinking agent is polycaprolactone-based polythiol.

[0076] The initiator is ethyl 2,4,6-trimethylbenzoylphenylphosphonate.

[0077] The curing accelerator is benzoyl peroxide;

[0078] The leveling agent is an acrylic leveling agent;

[0079] The silane coupling agent is 3-glycidyl etheroxypropyltriethoxysilane;

[0080] Antioxidants include phosphites and other antioxidants;

[0081] The electronic-grade organic solvent is methyl 3-methoxypropionate.

[0082] Example 5: A transparent photoresist composition with low shrinkage and low vacuum outgassing, comprising the following raw materials in weight percentages: 2% modified cage-type polysilsesquioxane (POSS), 1% expanded monomer, 5% modified acrylic resin, 3% epoxy resin, 1% alcohol crosslinking agent, 1% initiator, 0.4% curing accelerator, 0.2% leveling agent, 4% silane coupling agent, 0.02% antioxidant, and 82.38% electronic grade organic solvent.

[0083] Modified cage-type polysilsesquioxane (POSS) has a cage-type structure with T8. The reactive groups attached to the Si atoms at the eight vertices of the modified cage-type polysilsesquioxane (POSS) are epoxy groups and epoxycyclohexylethyl groups, with a total of 6 epoxy groups.

[0084] The expanding monomer is a spirocyclic protocarbonate, specifically 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0085] Modified acrylic resin is a block polymer of polyacrylic acid. In addition to acryloyloxy and epoxy groups, the characteristic functional groups of modified acrylic resin also include cycloglycidyl ether groups.

[0086] The epoxy resin is hydantoin epoxy resin.

[0087] The thiol crosslinking agent is polycaprolactone-based polythiol.

[0088] The initiators are 2,4-diethylthioxanthanone and 1-chloro-4-propoxythioxanthanone.

[0089] The curing accelerator is benzoyl peroxide and its modified forms;

[0090] The leveling agent is an organosilicon-based leveling agent;

[0091] The silane coupling agent is β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane;

[0092] The antioxidant is a phosphite;

[0093] The electronic-grade organic solvent is methyl isobutyl ketone.

[0094] Example 6: Referring to Example 1, the modified cage-type polysilsesquioxane (POSS) has a cage-type structure with T8. The reactive groups attached to the Si atoms at the eight vertices of the modified cage-type polysilsesquioxane (POSS) are epoxy groups, epoxycyclohexylethyl groups, or glycidyl etheroxypropyl groups, wherein the number of epoxy groups is 1 to 8.

[0095] The expanding monomer is a spirocyclic protocarbonate, specifically 3,9-diethyl-3',9'-dihydroxymethyl-1,5,7,11-tetraoxaspiro[5,5]undecane. 3,9-Diethylidene-2,4,8,10-tetraoxaspiro[5,5]undecane 3,9-Divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane One or more of the following.

[0096] Modified acrylic resin is a block polymer of polyacrylic acid. In addition to acryloyloxy and epoxy groups, the characteristic functional groups of modified acrylic resin include at least one or more of cyclohexyl, phenyl, epoxy, cyclopentadienyl, oxetyl, dicyclopentyl, naphthyl, and glycidyl ether.

[0097] The epoxy resin is at least one or a mixture of several of the following: glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresolaldehyde epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, maleimide epoxy resin, and hydantoin epoxy resin.

[0098] The thiol crosslinking agent is at least one or a mixture of several of the following: trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetras(3-mercaptopropionate), 1,6-hexanedithiol, polyethylene glycol (PEG-200 / 400) dimercaptopropionate, and polycaprolactone polythiol.

[0099] The initiator is at least one or a mixture of several of the following: bis(4-tert-butylphenyl)iodohexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-thionylhexafluorophosphate, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-isopropylthioxanthonone, ethyl 4-dimethylaminobenzoate, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, methyl o-benzoylbenzoate, 2,4-diethylthioxanthonone, and 1-chloro-4-propoxythioxanthonone.

[0100] The curing accelerator is at least one or a mixture of several of the following: ionic curing accelerator, polycarbodiamine, tetramethyl sulfoxide, tetrabutylammonium fluoride, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, dihydrotrifluorotetrabutylammonium, triethylamine, 4-methylaminopyridine, 1,5,7-triazabicyclo[4.4.0]decene-5-ene, triphenylphosphine, n-butylphosphine, polyetheramine, benzoyl peroxide and its modified forms;

[0101] The leveling agent is at least one or a mixture of several of silicone-based leveling agents and acrylate-based leveling agents;

[0102] The silane coupling agent is at least one or a mixture of several of the following: γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-glycidyl ether oxypropyltrimethoxysilane, 3-glycidyl ether oxypropyltriethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, γ-isocyanate propyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0103] The antioxidant is at least one or a mixture of several antioxidants such as aromatic amines, hindered phenols, thioethers, and phosphites;

[0104] The electronic-grade organic solvent is one or a mixture of several solvents selected from propylene glycol methyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, propylene glycol diacetate, 3-methoxybutylacetate, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, methyl N-pentyl ketone, methyl isobutyl ketone, etc.

[0105] Comparative Example 1: Referring to the formulation of Example 1, the expanding monomer was replaced with a highly functional acrylate monomer, such as dipentaerythritol hexaacrylate, which can also participate in click chemistry, while the proportions of the other components remained unchanged.

[0106] Comparative Example 2: Referring to the formulation of Example 3, the modified cage-like polysilsesquioxane was replaced with a conventional chain-like organosilicon resin with epoxy groups at the end, while the proportions of the other components remained unchanged.

[0107] Example 7: A method for preparing a curable coating from a transparent photoresist composition with low shrinkage and low vacuum degassing, comprising the following steps: taking modified cage-type polysilsesquioxane, expanding monomer, modified acrylic resin, epoxy resin, thiol crosslinking agent, initiator, curing accelerator, leveling agent, silane coupling agent, antioxidant, and electronic-grade organic solvent according to the formulation of Example 1, and mixing them evenly to obtain a transparent composition, then coating, VCD, and pre-baking to obtain a film surface, and then performing dual curing of photocuring and thermocuring to obtain a cured coating.

[0108] When mixing evenly, first mix 50% of the electronic-grade organic solvent with the remaining raw materials evenly. During mixing, disperse using a high-speed disperser at 1000 rpm for 20 minutes. Then, mix in the remaining electronic-grade organic solvent and mix evenly. During mixing, disperse using a high-speed disperser at 1500 rpm for 5 minutes. During coating, coat the transparent composition onto the substrate, and then pre-bake using a VCD vacuum to evaporate the solvent and obtain the film surface. During light curing, expose using a 2 kW high-pressure mercury lamp at 300 mJ. During thermosetting, bake at 80°C for 1 hour.

[0109] Example 8: A method for preparing a curable coating from a transparent photoresist composition with low shrinkage and low vacuum degassing, comprising the following steps: taking modified cage-type polysilsesquioxane, expanding monomer, modified acrylic resin, epoxy resin, thiol crosslinking agent, initiator, curing accelerator, leveling agent, silane coupling agent, antioxidant, and electronic-grade organic solvent according to the formulation of Example 2, and mixing them evenly to obtain a transparent composition, then coating, VCD, and pre-baking to obtain a film surface, and then obtaining a cured coating through photocuring and thermocuring.

[0110] When mixing evenly, first mix 60% of the electronic-grade organic solvent with the remaining raw materials evenly. During mixing, disperse using a high-speed disperser at 1200 rpm for 25 minutes. Then, mix in the remaining electronic-grade organic solvent and mix evenly. During mixing, disperse using a high-speed disperser at 2000 rpm for 7 minutes. During coating, coat the transparent composition onto the substrate, and then pre-bake under VCD vacuum to evaporate the solvent and obtain the film surface. During light curing, expose using a 2 kW high-pressure mercury lamp at 600 mJ. During thermosetting, bake at 100°C for 1 hour.

[0111] Example 9: A method for preparing a curable coating from a transparent photoresist composition with low shrinkage and low vacuum degassing, comprising the following steps: taking modified cage-type polysilsesquioxane, expanding monomer, modified acrylic resin, epoxy resin, thiol crosslinking agent, initiator, curing accelerator, leveling agent, silane coupling agent, antioxidant, and electronic-grade organic solvent according to the formulation of Example 3, and mixing them evenly to obtain a transparent composition, then coating, VCD, and pre-baking to obtain a film surface, and then obtaining a cured coating through photocuring and thermocuring.

[0112] When mixing evenly, first mix 65% of the electronic-grade organic solvent with the remaining raw materials evenly. During mixing, disperse using a high-speed disperser at 1300 rpm for 28 minutes. Then, mix in the remaining electronic-grade organic solvent and mix evenly. During mixing, disperse using a high-speed disperser at 2200 rpm for 8 minutes. During coating, coat the transparent composition onto the substrate, and then pre-bake using a VCD vacuum to evaporate the solvent and obtain the film surface. During light curing, expose using a 2 kW high-pressure mercury lamp at 800 mJ. During thermosetting, bake at 110°C for 1 hour.

[0113] Example 10: A method for preparing a curable coating from a transparent photoresist composition with low shrinkage and low vacuum degassing, comprising the following steps: taking modified cage-type polysilsesquioxane, expanding monomer, modified acrylic resin, epoxy resin, thiol crosslinking agent, initiator, curing accelerator, leveling agent, silane coupling agent, antioxidant, and electronic-grade organic solvent according to the formulation of Example 4, and mixing them evenly to obtain a transparent composition, then coating, VCD, and pre-baking to obtain a film surface, and then obtaining a cured coating through photocuring and thermocuring.

[0114] When mixing evenly, first mix 70% of the electronic-grade organic solvent with the remaining raw materials evenly. During mixing, disperse using a high-speed disperser at 1500 rpm for 30 minutes. Then, mix in the remaining electronic-grade organic solvent and mix evenly. During mixing, disperse using a high-speed disperser at 2500 rpm for 10 minutes. During coating, coat the transparent composition onto the substrate, and then pre-bake using a VCD vacuum to evaporate the solvent and obtain the film surface. During light curing, use a 2 kW high-pressure mercury lamp to expose the film at 1000 mJ. During thermosetting, bake at 120°C for 1 hour.

[0115] Comparative Example 3: Referring to Example 7, the materials were taken and prepared according to the formulation of Comparative Example 1.

[0116] Comparative Example 4: Referring to Example 7, the materials were taken and prepared according to the formulation of Comparative Example 2.

[0117] Table 1. Test results of main performance of transparent composite photoresist coating on ordinary glass substrate.

[0118]

[0119] Table 2. Test results of main performance of transparent composite photoresist coating on CF substrate.

[0120]

[0121] The test conditions, equipment methods, and judgment criteria for each test item are as follows:

[0122] 1. Hardness test: A fully automatic pencil hardness tester, model ZJ-3086, was used, and the standard was GB / T6739-2006. Each sample was tested three times, and the judgment standard was from 6B to BH to 6H, with the hardness gradually increasing.

[0123] 2. Dielectric constant test: Dielectric constant measuring instrument.

[0124] 3. Voltage Hold-up Rate (VHR) Test: The test equipment is the Espec SU-242 VHR tester. The VHR value is recorded at 5V-60Hz-60℃. The higher the VHR value, the lower the power loss and the smaller the impact on the normal deflection of the liquid crystal.

[0125] 4. Heat resistance test: The test equipment is TG 8121Thermo PlusEVO2. Weigh about 10g of the transparent composite photoresist cured coating. Heating process: 25℃→150℃, heating rate 10℃ / min, hold for 20min, record the weight loss rate L1 at this time. Then continue to heat to 230℃, heating rate 5℃ / min, hold for 180min, record the weight loss rate L2 at this time. The value of L2-L1 is outgassing. The lower the outgassing, the better.

[0126] 5. Test method and equipment for hygroscopicity: Prepare ordinary glass substrates measuring 10cm × 9cm with a 2.5µm cured coating from each embodiment. Soak in water for 1 hour, then dry and test. Use a Vacuum Measuring System GCV2000, set the bottom pressure to 0.003 Torr, and fix the initial pressure to 700 Torr. First, test the time to reach the bottom pressure for the blank glass, then test the time to reach the bottom pressure for the sample. Use the difference ΔT between the two as the criterion; the smaller ΔT is, the lower the hygroscopicity.

[0127] 6. Determination of residual film rate: The film thickness after pre-baking is recorded as T1, and the film thickness after exposure and heat curing is recorded as T2. The residual film rate T = T2 / T1. Four diagonal positions near the center of the same piece of glass are taken, and the residual film rate is calculated and the average value T is taken. The equipment used to measure the film thickness is a BRUKER probe surface profiler.

[0128] 7. Degree of Planarization (DOP) Test: The difference in film thickness of the CF substrate before and after coating with transparent photoresist is measured using a film thickness gauge, and the percentage of the film thickness difference to the film thickness before coating with transparent photoresist is calculated. The higher the DOP, the better the planarization capability.

[0129] 8. Masking test: Prepare a CF substrate with a transparent photoresist coating, drop 100 μL of NMP onto the substrate again and seal it, heat it at 180 °C for 15 min, rinse the substrate to obtain the rinsing solution, and then use a UV spectrophotometer to measure the absorbance of the rinsing solution at 305 nm.

[0130] 9. Contrast test: The test equipment used was the CONTRAST TESTERCT-1 from TSUBOSAKA ELECTRIC, and the light source was full-band.

[0131] As can be seen from the test results in Tables 1 and 2 above, in the formulation of Example 7, the modified cage-type polysilsesquioxane (POSS) has only one epoxy group, and the content of the expanding monomer is also relatively small. However, the reactive functional groups of the whole system reach a relatively suitable ratio. The double bonds of thiol and acrylic resin can be rapidly polymerized under low-energy ultraviolet light irradiation to form a preliminary three-dimensional network structure. Later, under the efficient thermal initiation of the ionic curing accelerator, even at a relatively low temperature of 80°C, the epoxy groups of the expanding monomer and POSS will undergo ring-opening polymerization and complete curing, forming a denser three-dimensional cross-linked network. This results in the transparent composition photoresist coating having an extremely low shrinkage rate and also reduces outgassing from the source. In the formulation of Example 8, the contents of modified cage-type polysilsesquioxane (POSS) and expanding monomers are relatively high. The pentaerythritol tetra(3-mercaptopropionate) crosslinking agent used has a high number of thiol groups. Following the same "click chemistry" reaction principle, this generally increases the packing density between molecules, enhances the crosslinking density, and improves the thermal stability of the material. The relatively high content of expanding monomers results in extremely low shrinkage of the entire system. Simultaneously, the curing accelerator polycarbodiamine can, to some extent, slow down the degradation reaction of ester bonds, further reducing the risk of small molecule leakage when the material is heated at high temperatures, thus achieving low outgassing performance. While the ring-opening reaction of epoxy causes some shrinkage, it is relatively low. The presence of expanding monomers makes the entire coating both dense and virtually free of significant shrinkage. In the formulation of Example 9, the selected 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane expanding monomer has both a spirocyclic ring and a double bond, resulting in higher reactivity. Furthermore, the number of epoxy groups at the POSS terminal reaches its maximum, allowing for a moderate thermosetting temperature. The "click reaction" dominates, and the volume expansion caused by the ring-opening of the expanding monomer during thermosetting effectively compensates for the volume shrinkage during UV curing, achieving extremely low net volume shrinkage. The different chemical cross-linking structures formed by the two curing methods interpenetrate and intertwine, forming an extremely dense and low-branched three-dimensional interpenetrating network. Combined with the barrier effect of POSS, this minimizes the decomposition and overflow of small molecules at high temperatures, achieving low outgassing. In the formulation of Example 10, although the content of modified cage-type polysilsesquioxane (POSS) and expanding monomer is relatively low, and the solid content is low, the expanding monomer also has double bonds and high activity. On the other hand, from the perspective of curing conditions, the UV curing energy is relatively higher and the thermal curing temperature is also higher, so the curing will be more complete. The moisture absorption and dielectric constant of the entire coating have achieved satisfactory results, and the shrinkage rate and outgassing performance are excellent. At the same time, the low solid content of the product is also conducive to cost control.In Comparative Example 3, the expanding monomer was replaced with the highly functional monomer dipentaerythritol hexaacrylate. Although this monomer can also participate in click chemistry, it is dendritic with more crosslinking points. After reacting with thiol groups, it causes severe shrinkage. Although the low shrinkage caused by the participation of other epoxy groups in the later reaction cannot offset the high shrinkage caused by dipentaerythritol hexaacrylate, small molecule monomers are easily left behind during curing, and its outgassing and hygroscopicity are not satisfactory. In Comparative Example 4, the modified cage-like polysilsesquioxane was replaced with a conventional chain silicone resin with epoxy groups at the end. Although both are silicone resins and can maintain good dielectric properties, the pure chain silicone resin is too flexible, the material is relatively soft, the tensile strength is low, and the hardness does not meet the relatively high requirements. In addition, the chain is prone to entanglement, which leads to incomplete reaction, and its outgassing and contrast are also affected to a certain extent. Overall, Examples 7-10 all utilize the addition of modified cage-type polysilsesquioxane and expanding monomers, along with appropriate compatibility with other raw materials, to achieve the desired product. By employing the "click chemistry" reaction principle and a photothermal dual-curing mechanism, the product not only maintains the high hardness, high thermal stability, high planarization capability, high barrier properties, low moisture absorption, and low dielectric constant of the transparent photoresist coating, but also exhibits excellent low shrinkage and low outgassing. This improves the yield of LCD products, achieving energy conservation, emission reduction, cost reduction, and efficiency improvement, while enhancing product competitiveness. The low shrinkage of the transparent photoresist coating also broadens the development prospects of this material in other panel manufacturing processes such as OLED, demonstrating wide-ranging application potential.

[0132] The described embodiments are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. A transparent photoresist composition with low shrinkage and low vacuum degassing, characterized in that, The raw materials include the following percentages by weight: 1-5% modified cage-type polysilsesquioxane (POSS), 1-5% expanding monomer, 1-5% modified acrylic resin, 1-5% epoxy resin, 1-5% thiol crosslinking agent, 1-5% initiator, 0.1-3% curing accelerator, 0.2-0.5% leveling agent, 0.1-5% silane coupling agent, 0.01-0.2% antioxidant, and 80-90% electronic-grade organic solvent; modified cage-type polysilsesquioxane (P... OSS has a cage-like structure with T8. The reactive groups attached to the Si atoms at the eight vertices of the modified cage-like polysilsesquioxane (POSS) are epoxy, epoxycyclohexylethyl, or glycidyl etheroxypropyl, wherein the number of epoxy groups is 1 to 8; the expanding monomer is a spirocyclic protocarbonate, and the spirocyclic protocarbonate is 3,9-diethyl-3',9'-dihydroxymethyl-1,5,7,11-tetraoxaspiro[5,5]undecane ( ), 3,9-diethylidene-2,4,8,10-tetraoxaspiro[5,5]undecane ( ), 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane ( The modified acrylic resin is at least one or a mixture of several of the following: the modified acrylic resin is a block polymer of polyacrylic acid including acryloyloxy and epoxy groups.

2. The low-shrinkage and low-vacuum degassing transparent composition photoresist according to claim 1, characterized in that, The modified acrylic resin is a block polymer of polyacrylic acid. In addition to acryloyloxy and epoxy groups, the characteristic functional groups of the modified acrylic resin include at least one or more of cyclohexyl, phenyl, epoxy, cyclopentadienyl, oxetyl, dicyclopentyl, naphthyl, and glycidyl ether.

3. The low-shrinkage and low-vacuum degassing transparent composition photoresist according to claim 1, characterized in that, The epoxy resin is at least one or a mixture of several of the following: glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol aldehyde epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, maleimide epoxy resin, and hydantoin epoxy resin.

4. The low-shrinkage and low-vacuum degassing transparent composition photoresist according to claim 1, characterized in that, The thiol crosslinking agent is at least one or a mixture of several of the following: trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetras(3-mercaptopropionate), 1,6-hexanedithiol, polyethylene glycol dimercaptopropionate, and polycaprolactone polythiol; the polyethylene glycol in the polyethylene glycol dimercaptopropionate is PEG-200 or PEG-400.

5. The low-shrinkage and low-vacuum-degassing transparent composition photoresist according to claim 1, characterized in that, The initiator is at least one or a mixture of several of the following: bis(4-tert-butylphenyl)iodohexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-thionylhexafluorophosphate, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-isopropylthioxanthonone, ethyl 4-dimethylaminobenzoate, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, methyl o-benzoylbenzoate, 2,4-diethylthioxanthonone, and 1-chloro-4-propoxythioxanthonone.

6. The low-shrinkage and low-vacuum-degassing transparent composition photoresist according to claim 1, characterized in that, The curing accelerator is at least one or a mixture of several of the following: ionic curing accelerator, polycarbodiamine, tetramethyl sulfoxide, tetrabutylammonium fluoride, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, dihydrotrifluorotetrabutylammonium, triethylamine, 4-methylaminopyridine, 1,5,7-triazabicyclo[4.4.0]decene-5-ene, triphenylphosphine, n-butylphosphine, polyetheramine, benzoyl peroxide and its modifiers; The leveling agent is at least one or a mixture of several of the following: silicone leveling agents and acrylate leveling agents; The silane coupling agent is at least one or a mixture of several of the following: γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-glycidyl ether oxypropyltrimethoxysilane, 3-glycidyl ether oxypropyltriethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, γ-isocyanate propyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The antioxidant is at least one or a mixture of several of the following: aromatic amines, hindered phenols, thioethers, and phosphites; The electronic-grade organic solvent is one or a mixture of several of the following: propylene glycol methyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, propylene glycol diacetate, 3-methoxybutylacetate, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, methyl N-pentyl ketone, and methyl isobutyl ketone.

7. A method for preparing a cured coating of a transparent composition photoresist with low shrinkage and low vacuum degassing as described in any one of claims 1 to 6, characterized in that, Includes the following steps: According to the formula, take modified cage-type polysilsesquioxane, expanding monomer, modified acrylic resin, epoxy resin, thiol crosslinking agent, initiator, curing accelerator, leveling agent, silane coupling agent, antioxidant, and electronic grade organic solvent, mix them evenly to obtain a transparent composition, then coat it, VCD it, and pre-bake it to obtain a film surface, and then cure it by light curing and heat curing to obtain a cured coating.

8. The method for preparing a cured coating using a transparent photoresist composition with low shrinkage and low vacuum degassing according to claim 7, characterized in that, When mixing evenly, first mix 50-70% of the electronic-grade organic solvent with the remaining raw materials evenly. During mixing, disperse using a high-speed disperser at 1000-1500 rpm for 20-30 minutes. Then, mix in the remaining electronic-grade organic solvent and mix evenly. During mixing, disperse using a high-speed disperser at 1500-2500 rpm for 5-10 minutes. During coating, coat the transparent composition onto the substrate, and then pre-bake under VCD vacuum to evaporate the solvent and obtain the film surface. During light curing, use a 2kW high-pressure mercury lamp to expose the film at 300-1000mJ. During thermosetting, bake at 80-120℃ for 1 hour.

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