Euv oxidation easy-clean coating layer, preparation method and application thereof

Abstract

The application discloses an EUV oxidizable easy-to-clean coating layer and a preparation method and application thereof, and relates to the technical field of glass production. The technical scheme is as follows: the coating layer comprises the following components in percentage by mass: 5-15% of tetrabutyl titanate, 10-20% of a photosensitive resin polymer matrix, 1-3% of a surfactant, 2-5% of a leveling agent, 2-5% of a defoaming agent and 65-80% of a solvent. The coating layer can replace traditional spacing paper, effectively protects the surface of a glass substrate, can be rapidly oxidized and degraded under EUV light irradiation, is easy to clean, and realizes convenient and residue-free cleaning effect.

Description

Technical Field

[0001] This invention relates to the field of glass production technology, specifically to an EUV oxidation easy-to-clean coating layer, its preparation method, and its application. Background Technology

[0002] In the production of display devices such as TFT-LCDs, the glass substrate is a critical raw material, and its quality directly affects the performance and yield of the final product. Therefore, taking effective protective measures during the transportation, storage, and processing of glass substrates is crucial. These measures aim to prevent scratches, contamination, and other quality problems on the glass substrate surface, ensuring the smooth operation of the production process.

[0003] Currently, spacer paper is commonly used as an insulating material in the production process to isolate glass substrates and prevent direct contact between them. While traditional spacer paper can protect TFT glass substrates to some extent, it also has several drawbacks: First, spacer paper is expensive, increasing production costs; second, when introducing glass substrates into downstream processes, spacer paper needs to be removed manually or mechanically, which is complex and reduces production efficiency; most importantly, spacer paper may introduce additional contamination during use, affecting the cleanliness of the glass substrates.

[0004] With the development of display technology, the requirements for glass substrates in panel manufacturing processes such as ARRAY (array) and CF (color filter) are becoming increasingly stringent. Before these two key processes, the glass substrate needs to be irradiated with EUV to achieve precise patterning. After irradiation, certain contaminants remain on the surface of the glass substrate, necessitating cleaning. Therefore, developing a coating layer that is compatible with EUV cleaning processes and easy to clean has become a new direction for glass substrate packaging. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide an EUV oxidation easy-to-clean coating layer, its preparation method and application. The coating layer can replace the traditional spacer paper, effectively protect the surface of the glass substrate, and can be rapidly oxidized and degraded under EUV light irradiation, making it easy to clean and achieving a convenient and residue-free cleaning effect.

[0006] The technical solution of this invention is as follows:

[0007] In a first aspect, the present invention provides an EUV oxidation easy-to-clean coating layer comprising the following components by weight percentage: 5-15% tetrabutyl titanate, 10-20% photosensitive resin polymer matrix, 1-3% surfactant, 2-5% leveling agent, 2-5% defoamer, and 65-80% solvent.

[0008] Among them, the photosensitive metal compound tetrabutyl titanate and the photosensitive resin polymer matrix can rapidly undergo an oxidation reaction under EUV light irradiation, leading to the destruction of the coating layer structure and making it easier to clean. Simultaneously, the photosensitive resin polymer matrix also provides good stability and adhesion to the coating layer, ensuring that the coating layer will not peel off or be damaged during normal use. Additives such as surfactants, leveling agents, and defoamers can improve the stability of the coating solution and the coating effect.

[0009] Preferably, the photosensitive resin polymer matrix is ​​one or more of polymethyl methacrylate, polyvinyl cycloacetal styrene pyridinium salt resin, and polyimide resin.

[0010] Preferably, the surfactant is sodium p-dodecyl sulfate.

[0011] Preferably, the leveling agent is sodium p-perfluorononoxybenzenesulfonate.

[0012] Preferably, the defoamer is polyoxypropylene ethylene glycerol.

[0013] Preferably, the solvent is propylene glycol methyl ether acetate.

[0014] Secondly, the present invention provides a method for preparing the above-mentioned EUV oxidation easy-to-clean coating layer, comprising the following steps:

[0015] S1 mixes all components except the solvent and dissolves them in the solvent to form a uniform coating solution;

[0016] S2 applies the coating solution evenly to the surface of the glass substrate;

[0017] S3 solidifies the coating solution onto the surface of the glass substrate to form a coating layer.

[0018] Preferably, in step S2, the coating solution is applied by spin coating, spray coating, or dip coating.

[0019] Preferably, in step S3, the curing method of the coating solution is heating, ultraviolet curing, or natural drying.

[0020] Thirdly, the present invention provides the application of the above-mentioned EUV oxidation easy-to-clean coating layer, wherein the coating layer replaces the spacer paper as the isolation material between glass substrates, and when it needs to be removed, it can be oxidized and degraded by EUV light irradiation before cleaning.

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] The coating layer of this invention has three main advantages: First, it effectively isolates airborne dust, moisture, and other contaminants, protecting the surface of the TFT glass substrate and providing excellent protection against damage during transportation, storage, and processing. Second, it is compatible with EUV cleaning processes. Under EUV light irradiation, the metal compounds and photosensitive resin polymer matrix in the coating layer rapidly oxidize, causing the coating layer structure to break down and become easier to clean. It can be completely removed through simple cleaning steps (such as water washing or air blowing) without complex processes. Third, it has lower costs and eliminates the need for manual or mechanical removal of spacers, simplifying operation and improving production efficiency while reducing costs. Therefore, using the coating layer of this invention to replace traditional spacers for the packaging and transportation of TFT glass substrates not only reduces material costs but also avoids the contamination problems that spacers may introduce. Furthermore, during subsequent customer processing, the coating layer rapidly oxidizes under EUV cleaning, becoming easy to clean and achieving a fast, residue-free cleaning effect, thus improving production efficiency and product quality. Detailed Implementation

[0023] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention.

[0024] Example 1

[0025] The EUV oxidation easy-clean coating layer of this embodiment comprises the following components by weight percentage: 10% tetrabutyl titanate, 13% polymethyl methacrylate, 72% propylene glycol methyl ether acetate, 2% sodium p-dodecyl sulfate, 2% sodium p-perfluorononoxybenzenesulfonate, and 1% polyoxypropylene ethylene glycerol.

[0026] Example 2

[0027] The EUV oxidation easy-clean coating layer of this embodiment comprises the following components by weight percentage: 5% tetrabutyl titanate, 13% polymethyl methacrylate, 77% propylene glycol methyl ether acetate, 2% sodium p-dodecyl sulfate, 2% sodium p-perfluorononoxybenzenesulfonate, and 1% polyoxypropylene ethylene glycerol.

[0028] Example 3

[0029] The EUV oxidation easy-clean coating layer of this embodiment comprises the following components by weight percentage: 15% tetrabutyl titanate, 13% polymethyl methacrylate, 67% propylene glycol methyl ether acetate, 2% sodium p-dodecyl sulfate, 2% sodium p-perfluorononoxybenzenesulfonate, and 1% polyoxypropylene ethylene glycerol.

[0030] Example 4

[0031] The EUV oxidation easy-clean coating layer of this embodiment comprises the following components by weight percentage: 10% tetrabutyl titanate, 13% polyvinyl cycloacetal styrene pyridinium salt resin, 72% propylene glycol methyl ether acetate, 2% sodium p-dodecyl sulfate, 2% sodium p-perfluorononoxybenzenesulfonate, and 1% polyoxypropylene ethylene glycerol.

[0032] Example 5

[0033] The EUV oxidation easy-clean coating layer of this embodiment comprises the following components by weight percentage: 10% tetrabutyl titanate, 13% polyimide resin, 72% propylene glycol methyl ether acetate, 2% sodium p-dodecyl sulfate, 2% sodium p-perfluorononoxybenzenesulfonate, and 1% polyoxypropylene ethylene glycerol.

[0034] The preparation methods of the coating layers in Examples 1-5 include the following steps:

[0035] S1 mixes all components except the solvent at room temperature and dissolves them in the solvent, stirring thoroughly until a uniform and transparent coating solution is formed; the viscosity of the coating solution at 20°C is 2.5 mPa·s to ensure uniformity and leveling during coating.

[0036] S2 prepares a 10cm×10cm TFT glass substrate after cleaning and drying, ensuring that the surface is free of dust, oil, and other impurities. The coating solution is then uniformly coated onto the surface of the TFT glass substrate using a spin coating method at a speed of 221 rpm and a spin coating time of 8 seconds.

[0037] S3 places the TFT glass substrate coated with the coating solution on a heating stage and heats it at 250°C for 2 minutes to solidify it, so that the coating solution forms a uniform and dense coating layer on the surface of the TFT glass substrate, with a coating layer thickness of about 2μm.

[0038] Comparative Example 1

[0039] Comparative Example 1 uses only polycarbonate (PC) as the coating layer material.

[0040] The preparation of the coating layer includes the following steps:

[0041] S1 dissolves PC in dichloromethane solvent to form a coating solution with a viscosity of 2.5 mPa·s at 20°C.

[0042] S2 uses spin coating to uniformly coat the coating solution onto the surface of the TFT glass substrate, with a spin coating speed of 221 rpm and a spin coating time of 8 s.

[0043] S3 places the TFT glass substrate coated with the coating solution on a heating stage and heats it at 150°C for 2 minutes to solidify it, so that the coating solution forms a uniform and dense coating layer on the surface of the TFT glass substrate, with a coating layer thickness of about 2μm.

[0044] Comparative Example 2

[0045] Comparative Example 2 used only polyethylene terephthalate (PET) film containing silver nanoparticles (10%) as the coating layer, with a coating layer thickness of approximately 2 μm.

[0046] The coating layer is prepared by directly attaching the thin film to the surface of the TFT glass substrate.

[0047] Comparative Example 3

[0048] Comparative Example 3 uses traditional spacer paper as the separating material.

[0049] The method of use is as follows: place the spacer paper directly between the TFT glass substrates to protect and separate the TFT glass substrates.

[0050] The coating layer of Comparative Example 4 comprises the following components by weight percentage: 20% polymethyl methacrylate, 75% propylene glycol methyl ether acetate, 2% sodium p-dodecyl sulfate, 2% sodium p-perfluorononoxybenzenesulfonate, and 1% polyoxypropylene ethylene glycerol.

[0051] The coating layer of Comparative Example 5 comprises the following components by weight percentage: 15% tetrabutyl titanate, 80% propylene glycol methyl ether acetate, 2% sodium p-dodecyl sulfate, 2% sodium p-perfluorononoxybenzenesulfonate, and 1% polyoxypropylene ethylene glycerol.

[0052] The performance of the coatings in Examples 1-5 and Comparative Examples 1-5 was tested using the following methods:

[0053] Pencil hardness: Take 3 clean TFT glass substrates coated with the coating layer from Examples 1-5, Comparative Examples 1-2, and Comparative Examples 4-5, and test the hardness of the coating layer according to the test method of ASTM D3363-22 "Standard Test Method for Determination of Hardness of Thin Films by Pencil Test".

[0054] Coating removal rate: Three cleaned TFT glass substrates coated with the coating layer from Examples 1-5, Comparative Examples 1-2, and Comparative Examples 4-5 were taken. The thickness of the coating layer was measured and recorded using a film thickness gauge. The substrates were then irradiated under an EUV light source for 30 seconds, rinsed with deionized water, dried, and the coating layer thickness was measured again. The coating removal rate was calculated to determine the coating layer removal status. The formula for calculating the coating removal rate is as follows:

[0055]

[0056] The performance test results of the coating layers in Examples 1-5, Comparative Examples 1-2, and Comparative Examples 4-5 are shown in Table 1:

[0057] Table 1. Performance test results of the coating layers in Examples 1-5, Comparative Examples 1-2, and Comparative Examples 4-5.

[0058] Example 1 6H 100％ Example 2 5H 100％ Example 3 5H 100％ Example 4 3H 100％ Example 5 4H 100％ Comparative Example 1 4H 3.2％ Comparative Example 2 2H 21.3％ Comparative Example 4 4H 93.6％ Comparative Example 5 2H 100％

[0059] As can be seen from Table 1:

[0060] In Examples 1-3, the coating removal rate reached 100%. However, with the increase of tetrabutyl titanate content, the pencil hardness of the coating initially increased and then decreased. This is because when the tetrabutyl titanate content is low, it can undergo a certain cross-linking reaction with polymethyl methacrylate (PMMA). This cross-linking reaction makes the connection between polymer molecular chains tighter, restricts the movement of molecular chains, makes the polymer film structure more stable, and enhances its resistance to external forces, thereby increasing the hardness of the coating. However, when the tetrabutyl titanate content is too high, tetrabutyl titanate agglomeration occurs. The agglomerated tetrabutyl titanate forms an uneven dispersion in the coating, creating defects and stress concentration points. These defects and stress concentration points easily become weak points in the coating when subjected to external forces, thus leading to a decrease in the hardness of the coating.

[0061] In Example 4, the photosensitive resin polymer matrix is ​​polyvinyl cycloacetal styrene pyridinium salt resin, and the coating layer removal rate can also reach 100%. However, the coating layer hardness is not as good as that in Example 1. This is because: (1) Difference in molecular structure: PMMA in Example 1 has a relatively regular molecular structure and the molecular chains are arranged relatively tightly. This tight arrangement can provide a certain rigidity, resulting in higher hardness after film formation. However, the molecular structure of polyvinyl cycloacetal styrene pyridinium salt resin in Example 4 is relatively complex and loose, with a larger spacing between molecular chains. This makes it easier for the molecular chains to shift when subjected to external force, resulting in lower hardness. (2) Different degree of crosslinking: PMMA is more likely to form a certain degree of crosslinking structure during film formation. Crosslinking can enhance the intermolecular forces and improve the hardness and strength of the coating layer. However, due to its structural characteristics, polyvinyl cycloacetal styrene pyridinium salt resin has a lower degree of crosslinking under the same film formation conditions, resulting in lower hardness of the coating layer.

[0062] In Example 5, the photosensitive resin polymer matrix is ​​polyimide resin, and the coating layer removal rate can also reach 100%. However, the hardness of the coating layer is not as good as that in Example 1. This is because the PMMA in Example 1 has a relatively simple and regular molecular structure with a relatively tight molecular chain arrangement, which can form a more robust structure, thereby helping to improve the hardness after film formation. In contrast, the polyimide resin in Example 5 usually has a more complex molecular structure with some flexible segments or irregular structures, which makes the intermolecular bonding relatively weak and more prone to deformation under external force, resulting in a decrease in the hardness of the coating layer.

[0063] Furthermore, Comparative Example 1 uses only PC as the coating layer material. Although it has good hardness and can effectively protect the TFT glass substrate surface from scratches, it lacks EUV sensitivity and cannot be effectively cleaned using EUV light, resulting in difficult coating layer cleaning and requiring manual or mechanical removal. Comparative Example 2 uses only PET film containing a small amount of silver nanoparticles as the coating layer. Although silver nanoparticles have some sensitivity to EUV light, the hardness and coating layer removal rate of PET film are far inferior to the coating layer of this invention, thus also presenting cleaning difficulties. Comparative Example 3 uses traditional spacer paper as the isolation material without any coating layer. Although the spacer paper can protect the TFT glass substrate from damage during storage and transportation to some extent, it requires manual or mechanical removal when the glass substrate is introduced into the downstream factory process. This is inconvenient, and the spacer paper is mostly for single use and expensive, which not only increases production costs but also requires disposal after disposal, cannot be recycled, and will have a certain impact on the environment. Comparative Example 4, without tetrabutyl titanate, while possessing good hardness and effectively protecting the TFT glass substrate surface from scratches, suffers from low EUV sensitivity, hindering effective cleaning with EUV light. This results in incomplete cleaning of the coating layer, requiring increased EUV irradiation time for complete removal, thus increasing production costs. Comparative Example 5, without polymethyl methacrylate, achieves a 100% coating layer removal rate, but its post-coating hardness is poor, failing to effectively protect the TFT glass substrate surface from scratches.

Claims

1. The application of EUV oxidation easy-to-clean coating layers, characterized in that, The EUV oxidation easy-clean coating layer comprises the following components by weight percentage: 5-15% tetrabutyl titanate, 10-20% photosensitive resin polymer matrix, 1-3% surfactant, 2-5% leveling agent, 2-5% defoamer, and 65-80% solvent; the photosensitive resin polymer matrix is ​​one or more of polymethyl methacrylate, polyvinyl cycloacetal styrene pyridinium salt resin, and polyimide resin; the coating layer replaces the spacer paper as the isolation material between the glass substrates, and when it needs to be removed, it can be oxidized and degraded by EUV light irradiation before cleaning.

2. The application of the EUV oxidation easy-to-clean coating layer as described in claim 1, characterized in that, The leveling agent is sodium p-perfluorononoxybenzenesulfonate.

3. The application of the EUV oxidation easy-to-clean coating layer as described in claim 1, characterized in that, The defoamer is polyoxypropylene ethylene glycerol.

4. The application of the EUV oxidation easy-to-clean coating layer as described in claim 1, characterized in that, The solvent is propylene glycol methyl ether acetate.

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