A low-foaming glass substrate cleaning solution

Abstract

The application discloses a low-foam glass substrate cleaning solution, relates to the technical field of cleaning solutions, and comprises 25-40 parts by weight of dimethylbenzene, 20-35 parts by weight of propylene glycol methyl ether acetate, 10-20 parts by weight of n-butanol, 15-25 parts by weight of ethanol, 5-10 parts by weight of a wet dispersant and 1-4 parts by weight of an inhibitor; wherein the dimethylbenzene is alkyl-closed dimethylbenzene closed by alkyl; and the wet dispersant is a polydimethylsiloxane grafted / PLR-1900 wet dispersant. The application has the effect of significantly inhibiting foaming; the alkyl-closed dimethylbenzene in the application can effectively remove photoresist residues and grease, and cooperates with the wet dispersant to realize the effects of preventing contaminants from being re-stained and watermarks from being stained.

Description

Technical Field

[0001] This application relates to the field of cleaning fluid technology, and in particular to a low-foaming glass substrate cleaning fluid. Background Technology

[0002] As a core component of precision electronic devices, display panels, and other products, the surface cleanliness of glass substrates directly determines the performance and lifespan of the final product. Therefore, specialized cleaning solutions are required to thoroughly remove photoresist residue, grease, dust, and other contaminants from their surfaces. Glass substrate cleaning solutions must balance low foaming, high cleaning power, high stability, and environmental friendliness, and be compatible with industrial cleaning processes such as spraying and ultrasonic cleaning. This prevents foam overflow and contaminant re-adhesion during cleaning, while also preventing corrosion or residue on the glass substrate, thus meeting the stringent requirements of precision cleaning.

[0003] In existing technologies, the composition of glass substrate cleaning solutions has become a relatively fixed system. Typical formulations, by weight, include: 25-40 parts of pure xylene, 20-35 parts of propylene glycol methyl ether acetate (PMA), 10-20 parts of n-butanol, and 15-25 parts of ethanol as solvents; 5-10 parts of PLR-1900 polyether wetting and dispersing agent, and 1-4 parts of organic corrosion inhibitors such as benzotriazoles and amine corrosion inhibitors; some formulations use pure HZSM-5 molecular sieves or strong corrosion catalysts such as aluminum trichloride and sulfuric acid to prepare simple modified xylene to replace pure xylene.

[0004] However, existing glass substrate cleaning solutions suffer from problems such as foaming and oxidation due to the high surface tension and strong active sites of pure xylene and its benzene ring in the solvent system. Furthermore, they exhibit poor compatibility with other components and are prone to stratification over long periods, leading to foam overflow and contaminant residue during cleaning, thus affecting cleaning uniformity. Simultaneously, existing modified xylene preparations rely on highly corrosive catalysts, causing equipment corrosion, generating large amounts of chlorine-containing wastewater, and requiring the addition of alkylating agents, resulting in a cumbersome and environmentally unfriendly process. In addition, insufficient wetting and dispersing agents lead to watermarks and oil stains on the substrate surface, affecting the cleanliness of the glass substrate and its subsequent processing performance, necessitating improvements. Summary of the Invention

[0005] In view of this, the purpose of this application is to provide a low-foaming glass substrate cleaning solution to significantly improve cleaning cleanliness and operational stability. The specific solution is as follows: A low-foaming glass substrate cleaning solution comprises 25-40 parts by weight of xylene, 20-35 parts by weight of propylene glycol methyl ether acetate, 10-20 parts by weight of n-butanol, 15-25 parts by weight of ethanol, 5-10 parts by weight of a wetting and dispersing agent, and 1-4 parts by weight of a corrosion inhibitor; wherein the xylene is an alkyl-blocked xylene; and the wetting and dispersing agent is polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent.

[0006] Preferably, the preparation method of the alkyl-blocked xylene includes step ① activating HZSM-5 molecular sieve and then purging with nitrogen to obtain a clean molecular sieve; step ② preheating and vaporizing xylene under a nitrogen atmosphere, controlling the reaction temperature at 340-380℃, the pressure at 1.0-1.8MPa, and the mass hourly space velocity at 1.5-2.5h. -1 The reaction time is 3-5 hours, and the product of self-disproportionation alkyl transfer reaction is obtained after the reaction. In step ③, the product of self-disproportionation alkyl transfer reaction is condensed, distilled to obtain the fraction, dried and filtered to obtain alkyl-blocked xylene.

[0007] Preferably: in step ①, the activation treatment is performed at a controlled temperature of 530-570℃, a heating rate of 2-5℃ / min, and calcination in air atmosphere for 3.5-4.5h, followed by cooling to room temperature; the nitrogen purging is performed at a controlled flow rate of 8-22mL / min and purging for 25-35min; in step ②, the preheating vaporization is performed at a controlled temperature of 150-180℃.

[0008] Preferably, in step ③, the condensation is performed by controlling the temperature at 55-75℃ and condensing to obtain a liquid material; the distillation is performed by controlling the distillation at atmospheric pressure and selecting the fraction at a temperature of 135-145℃ as the distillate material; the drying is performed by drying with anhydrous sodium sulfate for 2-4 hours; and the filtration is performed by filtering with a 0.22-0.45μm filter membrane to obtain alkyl-blocked xylene with a purity ≥94%.

[0009] Preferably, the HZSM-5 molecular sieve is a modified HZSM-5 molecular sieve, and the silicon-aluminum molar ratio is 50-100.

[0010] Preferably, the modification method of the modified HZSM-5 molecular sieve includes pretreatment, acid leaching modification, and washing and drying; the pretreatment includes pulverizing the HZSM-5 molecular sieve to 200-300 mesh, drying it at 110-120℃ for 2-4 hours to obtain pretreated molecular sieve; the acid leaching modification involves adding 0.2-2 mol / L nitric acid solution to the pretreated molecular sieve at a solid-liquid mass ratio of 1:5-10, mixing it, stirring and refluxing it at 60-80℃ for 3-5 hours, and then filtering to obtain modified molecular sieve; the washing and drying involves washing with deionized water until neutral, and then drying it at 110-120℃ for 2-4 hours.

[0011] Preferably, the preparation method of the polydimethylsiloxane graft / PLR-1900 wetting and dispersing agent includes end-group activation, hydrosilylation, and purification of PLR-1900 polyether polyol to obtain a modified wetting and dispersing agent with a grafting rate greater than 85%; the hydrosilylation includes adding 10-25% of terminal hydrogen-based polydimethylsiloxane by mass of PLR-1900 polyether polyol and stirring evenly, then adding 0.05-0.1% of Karstedt catalyst by mass of PLR-1900 polyether polyol at a controlled dropping rate of 0.01-0.02 parts / min, and reacting at 80-90℃ for 6-8 hours to obtain the addition wetting and dispersing agent.

[0012] Preferably, the end-group activation includes mixing PLR-1900 polyether polyol with anhydrous isopropanol at a mass ratio of 1.6-1.8:1, heating to 60-70°C, controlling the vacuum degree to -0.08 to -0.09 MPa for dehydration for 0.8-1.2 hours, then adding 0.1-0.3% of p-hydroxyanisole by mass of PLR-1900 polyether polyol, and stirring evenly to obtain an activated wetting and dispersing agent.

[0013] Preferably, the purification includes distilling the addition wetting and dispersing agent under reduced pressure at a controlled temperature of 70-80℃ and a pressure of 4-6kPa for 1-1.5h to obtain the modified wetting and dispersing agent.

[0014] Preferably, the preparation method includes preparing alkyl-blocked xylene and polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent separately, stirring alkyl-blocked xylene, propylene glycol methyl ether acetate, n-butanol and ethanol at room temperature and pressure for 8-12 minutes and mixing them evenly, then adding polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent and corrosion inhibitor, stirring for 12-18 minutes until completely dissolved, and finally filtering through a filter membrane to obtain the finished low-foaming glass substrate cleaning solution.

[0015] As can be seen from the above solutions, this application provides a low-foaming glass substrate cleaning solution, which has the following beneficial effects: 1. Alkyl-blocked xylene is prepared by self-disproportionation catalysis of HZSM-5 molecular sieve. The active sites of the benzene ring are blocked by alkyl groups, which reduces surface tension and foaming rate. In addition, the siloxane segments of polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent can spread rapidly at the gas-liquid interface, thereby destroying the stability of the foam liquid film. This allows it to work synergistically with alkyl-blocked xylene to avoid foam overflow and the entrainment of pollutants. 2. Strong dissolving power is achieved through alkyl-blocked xylene, which efficiently dissolves oily contaminants such as photoresist residue and grease on the surface of glass substrates; and polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent significantly improves the wettability of the cleaning solution, allowing it to spread quickly on the substrate surface, while stabilizing the dissolved contaminants and preventing re-adhesion, achieving dual-effect removal of polar and non-polar contaminants, and leaving no watermarks or oil spots after cleaning; 3. The modified HZSM-5 molecular sieve by acid leaching achieves the effects of optimized acid strength and pore structure, and improved catalytic selectivity. Moreover, the xylene self-disproportionation reaction is simple, the raw materials are controllable, and the process is simple and environmentally friendly, thus significantly reducing production costs. Detailed Implementation

[0016] The technical solutions described below in conjunction with the embodiments of this application will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of the embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0017] It should be mentioned that the number average molecular weight of the hydrogen-terminated polydimethylsiloxane in the embodiments of this application is 1000-2000, and the Si-H content is 0.5-1.0 mmol / g.

[0018] The following is a detailed description of a low-foaming glass substrate cleaning solution according to this application.

[0019] A low-foaming glass substrate cleaning solution comprises 25-40 parts by weight of xylene, 20-35 parts by weight of propylene glycol methyl ether acetate, 10-20 parts by weight of n-butanol, 15-25 parts by weight of ethanol, 5-10 parts by weight of wetting and dispersing agent, and 1-4 parts by weight of corrosion inhibitor.

[0020] In the embodiments of this application, the xylene is an alkyl-blocked xylene. The wetting and dispersing agent is polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent.

[0021] The preparation method of alkyl-blocked xylene includes the following steps: Step ① Activating HZSM-5 molecular sieve, controlling the activation temperature at 530-570℃ and the heating rate at 2-5℃ / min, calcining in air for 3.5-4.5h, cooling to room temperature, and then purging with nitrogen at a flow rate of 8-22mL / min for 25-35min to obtain clean molecular sieve; Step ② Preheating and vaporizing xylene, controlling the preheating and vaporization temperature at 150-180℃, and then reacting in a nitrogen atmosphere at a temperature of 340-380℃, a pressure of 1.0-1.8MPa, and a mass hourly space velocity of 1.5-2.5h. -1 The reaction time is 3-5 hours, and the product of the self-disproportionation alkyl transfer reaction is obtained after the reaction. In step ③, the product of the self-disproportionation alkyl transfer reaction is condensed at a controlled temperature of 55-75℃ to obtain a liquid material, distilled at atmospheric pressure and the fraction at a temperature of 135-145℃ is taken as the fraction material, dried with anhydrous sodium sulfate for 2-4 hours and filtered with a 0.22-0.45μm filter membrane to obtain alkyl-blocked xylene with a purity ≥94%.

[0022] It should be noted that the HZSM-5 molecular sieve in this application embodiment is a modified HZSM-5 molecular sieve, and the silicon-aluminum molar ratio is 50-100. The modification method of the modified HZSM-5 molecular sieve includes pretreatment, acid leaching modification, and washing and drying. The pretreatment includes pulverizing the HZSM-5 molecular sieve to 200-300 mesh, drying it at 110-120℃ for 2-4 hours to obtain the pretreated molecular sieve. The acid leaching modification involves adding 0.2-2 mol / L nitric acid solution to the pretreated molecular sieve at a solid-liquid mass ratio of 1:5-10, mixing it, stirring and refluxing it at a controlled temperature of 60-80℃ for 3-5 hours, and then filtering to obtain the modified molecular sieve. The washing and drying involves washing with deionized water until neutral, and then drying it at 110-120℃ for 2-4 hours.

[0023] Meanwhile, the preparation method of the polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent in the embodiments of this application includes end-group activation, hydrosilylation, and purification of PLR-1900 polyether polyol to obtain a modified wetting and dispersing agent with a grafting rate greater than 85%. End-group activation includes mixing PLR-1900 polyether polyol with anhydrous isopropanol at a mass ratio of 1.6-1.8:1, heating to 60-70°C, controlling the vacuum degree at -0.08 to -0.09 MPa for dehydration for 0.8-1.2 h, then adding 0.1-0.3% p-hydroxyanisole by mass of PLR-1900 polyether polyol, and stirring until homogeneous to obtain the activated wetting and dispersing agent. The hydrosilylation process involves adding 10-25% (by weight of PLR-1900 polyether polyol) of terminal hydrogen-based polydimethylsiloxane and stirring until homogeneous. Then, 0.05-0.1% (by weight of PLR-1900 polyether polyol) of Karstedt catalyst is added at a controlled dropping rate of 0.01-0.02 parts / min. The mixture is heated to 80-90℃ and reacted for 6-8 hours to obtain the addition wetting and dispersing agent. Purification involves subjecting the addition wetting and dispersing agent to vacuum distillation at a controlled temperature of 70-80℃ and a pressure of 4-6 kPa for 1-1.5 hours to obtain the modified wetting and dispersing agent.

[0024] The preparation method of the low-foaming glass substrate cleaning solution in this application embodiment includes first preparing alkyl-blocked xylene and polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent, stirring alkyl-blocked xylene, propylene glycol methyl ether acetate, n-butanol and ethanol at room temperature and pressure for 8-12 minutes and mixing them evenly, then adding polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent and corrosion inhibitor, stirring for 12-18 minutes until completely dissolved, and finally filtering through a filter membrane to obtain the finished low-foaming glass substrate cleaning solution.

[0025] Example 1 A low-foaming glass substrate cleaning solution comprises 25 parts by weight of xylene, 35 parts by weight of propylene glycol methyl ether acetate, 15 parts by weight of n-butanol, 18 parts by weight of ethanol, 5 parts by weight of wetting and dispersing agent, and 2 parts by weight of corrosion inhibitor.

[0026] In the embodiments of this application, the xylene is an alkyl-blocked xylene. The wetting and dispersing agent is polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent.

[0027] The preparation method of alkyl-blocked xylene includes the following steps: Step ① HZSM-5 molecular sieve is activated at a temperature of 530℃ and a heating rate of 2℃ / min. After calcination in air for 4.5 h, it is cooled to room temperature and then purged with nitrogen at a flow rate of 8 mL / min for 25 min to obtain clean molecular sieve; Step ② Xylene is preheated and vaporized at a temperature of 150℃, and then reacted in a nitrogen atmosphere at a temperature of 340℃, a pressure of 1.0 MPa, and a mass hourly space velocity of 1.5 h⁻¹. -1 The reaction time was 5 hours, and the product of the self-disproportionation alkyl transfer reaction was obtained after the reaction. In step ③, the product of the self-disproportionation alkyl transfer reaction was condensed at a controlled temperature of 55°C to obtain a liquid material, distilled at atmospheric pressure and the fraction at a temperature of 135°C was taken as the fraction material, dried with anhydrous sodium sulfate for 2 hours, and filtered with a 0.22 μm filter membrane to obtain alkyl-blocked xylene with a purity of ≥94%.

[0028] It should be noted that the HZSM-5 molecular sieve in this embodiment is a modified HZSM-5 molecular sieve, and the silicon-to-aluminum molar ratio is 50. The modification method of the modified HZSM-5 molecular sieve includes pretreatment, acid leaching modification, and washing and drying. The pretreatment includes pulverizing the HZSM-5 molecular sieve to 200 mesh and drying it at 110°C for 4 hours to obtain the pretreated molecular sieve. The acid leaching modification involves adding 0.2 mol / L nitric acid solution to the pretreated molecular sieve at a solid-liquid mass ratio of 1:5, mixing it, stirring and refluxing it at 60°C for 5 hours, and then filtering to obtain the modified molecular sieve. The washing and drying involves washing with deionized water until neutral, and then drying it at 110°C for 4 hours.

[0029] Meanwhile, the preparation method of the polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent in the embodiments of this application includes end-group activation, hydrosilylation, and purification of PLR-1900 polyether polyol to obtain a modified wetting and dispersing agent with a grafting rate greater than 85%. End-group activation includes mixing PLR-1900 polyether polyol with anhydrous isopropanol at a mass ratio of 1.6:1, heating to 60°C, controlling the vacuum degree at -0.08 MPa for dehydration for 1.2 h, then adding 0.1% p-hydroxyanisole (by mass of PLR-1900 polyether polyol), and stirring until homogeneous to obtain the activated wetting and dispersing agent. The hydrosilylation process involves adding 10% (by weight of PLR-1900 polyether polyol) of terminal hydrogen-based polydimethylsiloxane and stirring until homogeneous. Then, 0.05% (by weight of PLR-1900 polyether polyol) of Karstedt catalyst is added at a controlled dropping rate of 0.01 parts / min. The mixture is heated to 80°C and reacted for 8 hours to obtain the addition wetting and dispersing agent. Purification involves distilling the addition wetting and dispersing agent under reduced pressure (70°C, 4 kPa) for 1.5 hours to obtain the modified wetting and dispersing agent.

[0030] The preparation method of the low-foaming glass substrate cleaning solution in this application embodiment includes first preparing alkyl-blocked xylene and polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent, respectively; stirring alkyl-blocked xylene, propylene glycol methyl ether acetate, n-butanol and ethanol at room temperature and pressure for 8 minutes and mixing them evenly; then adding polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent and corrosion inhibitor, stirring for 12 minutes until completely dissolved; and finally filtering through a filter membrane to obtain the finished low-foaming glass substrate cleaning solution.

[0031] Example 2 A low-foaming glass substrate cleaning solution comprises 32 parts by weight of xylene, 26 parts by weight of propylene glycol methyl ether acetate, 14 parts by weight of n-butanol, 20 parts by weight of ethanol, 6 parts by weight of wetting and dispersing agent, and 2 parts by weight of corrosion inhibitor.

[0032] In the embodiments of this application, the xylene is an alkyl-blocked xylene. The wetting and dispersing agent is polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent.

[0033] The preparation method of alkyl-blocked xylene includes the following steps: Step ① HZSM-5 molecular sieve is activated at a temperature of 550℃ and a heating rate of 4℃ / min. After calcination in air for 4 hours, it is cooled to room temperature and then purged with nitrogen at a flow rate of 15mL / min for 30 minutes to obtain a clean molecular sieve; Step ② Xylene is preheated and vaporized at a temperature of 165℃. Then, under a nitrogen atmosphere, the reaction temperature is controlled at 360℃, the pressure at 1.3MPa, and the mass hourly space velocity at 2h⁻¹. -1 The reaction time was 4 hours, and the product of the self-disproportionation alkyl transfer reaction was obtained after the reaction. In step ③, the product of the self-disproportionation alkyl transfer reaction was condensed at a controlled temperature of 65°C to obtain a liquid material, distilled at atmospheric pressure and the fraction at a temperature of 140°C was taken as the fraction material, dried with anhydrous sodium sulfate for 3 hours and filtered with a 0.28 μm filter membrane to obtain alkyl-blocked xylene with a purity of ≥94%.

[0034] It should be noted that the HZSM-5 molecular sieve in this application embodiment is a modified HZSM-5 molecular sieve, and the silicon-to-aluminum molar ratio is 75. The modification method of the modified HZSM-5 molecular sieve includes pretreatment, acid leaching modification, and washing and drying. The pretreatment includes pulverizing the HZSM-5 molecular sieve to 220 mesh and drying it at 115°C for 3 hours to obtain the pretreated molecular sieve. The acid leaching modification involves adding 1 mol / L nitric acid solution to the pretreated molecular sieve at a solid-liquid mass ratio of 1:7, mixing it, stirring and refluxing it at 70°C for 4 hours, and then filtering to obtain the modified molecular sieve. The washing and drying involves washing with deionized water until neutral, and then drying it at 115°C for 3 hours.

[0035] Meanwhile, the preparation method of the polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent in the embodiments of this application includes end-group activation, hydrosilylation, and purification of PLR-1900 polyether polyol to obtain a modified wetting and dispersing agent with a grafting rate greater than 85%. End-group activation includes mixing PLR-1900 polyether polyol with anhydrous isopropanol at a mass ratio of 1.7:1, heating to 65°C, controlling the vacuum degree at -0.08 MPa for 1 hour to dehydrate, then adding 0.2% p-hydroxyanisole by mass of PLR-1900 polyether polyol, and stirring until homogeneous to obtain the activated wetting and dispersing agent. The hydrosilylation process involves adding 15% (by weight of PLR-1900 polyether polyol) of terminal hydrogen-based polydimethylsiloxane and stirring until homogeneous. Then, 0.07% (by weight of PLR-1900 polyether polyol) of Karstedt catalyst is added at a controlled dropping rate of 0.01 parts / min. The mixture is heated to 85°C and reacted for 7 hours to obtain the addition wetting and dispersing agent. Purification involves distilling the addition wetting and dispersing agent under reduced pressure (75°C, 5 kPa) for 1.2 hours to obtain the modified wetting and dispersing agent.

[0036] The preparation method of the low-foaming glass substrate cleaning solution in this application embodiment includes first preparing alkyl-blocked xylene and polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent, respectively; stirring alkyl-blocked xylene, propylene glycol methyl ether acetate, n-butanol and ethanol at room temperature and pressure for 10 min and mixing evenly; then adding polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent and corrosion inhibitor, stirring for 15 min until completely dissolved; and finally filtering through a filter membrane to obtain the finished low-foaming glass substrate cleaning solution.

[0037] Example 3 A low-foaming glass substrate cleaning solution comprises 40 parts by weight of xylene, 20 parts by weight of propylene glycol methyl ether acetate, 10 parts by weight of n-butanol, 16 parts by weight of ethanol, 10 parts by weight of wetting and dispersing agent, and 4 parts by weight of corrosion inhibitor.

[0038] In the embodiments of this application, the xylene is an alkyl-blocked xylene. The wetting and dispersing agent is polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent.

[0039] The preparation method of alkyl-blocked xylene includes the following steps: Step ① HZSM-5 molecular sieve is activated at a temperature of 570℃ and a heating rate of 5℃ / min. After calcination in air for 3.5 h, it is cooled to room temperature and then purged with nitrogen at a flow rate of 22 mL / min for 35 min to obtain clean molecular sieve; Step ② Xylene is preheated and vaporized at a temperature of 180℃, and then reacted in a nitrogen atmosphere at a temperature of 380℃, a pressure of 1.8 MPa, and a mass hourly space velocity of 2.5 h⁻¹. -1 The reaction time is 3 hours, and the product of self-disproportionation alkyl transfer reaction is obtained after the reaction. In step ③, the product of self-disproportionation alkyl transfer reaction is condensed at a controlled temperature of 75°C to obtain liquid material, distilled at atmospheric pressure and the fraction at a temperature of 145°C is taken as the fraction material, dried with anhydrous sodium sulfate for 2 hours and filtered with a 0.45μm filter membrane to obtain alkyl-blocked xylene with a purity of ≥94%.

[0040] It should be noted that the HZSM-5 molecular sieve in this application embodiment is a modified HZSM-5 molecular sieve, and the silicon-to-aluminum molar ratio is 100. The modification method of the modified HZSM-5 molecular sieve includes pretreatment, acid leaching modification, and washing and drying. The pretreatment includes pulverizing the HZSM-5 molecular sieve to 300 mesh and drying it at 120°C for 2 hours to obtain the pretreated molecular sieve. The acid leaching modification involves adding 2 mol / L nitric acid solution to the pretreated molecular sieve at a solid-liquid mass ratio of 1:10, mixing it, stirring and refluxing it at 80°C for 3 hours, and then filtering to obtain the modified molecular sieve. The washing and drying involves washing with deionized water until neutral, and then drying it at 120°C for 2 hours.

[0041] Meanwhile, the preparation method of the polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent in the embodiments of this application includes end-group activation, hydrosilylation, and purification of PLR-1900 polyether polyol to obtain a modified wetting and dispersing agent with a grafting rate greater than 85%. End-group activation includes mixing PLR-1900 polyether polyol with anhydrous isopropanol at a mass ratio of 1.8:1, heating to 70°C, controlling the vacuum degree at -0.09 MPa for dehydration for 0.8 h, then adding 0.3% p-hydroxyanisole (by mass of PLR-1900 polyether polyol), and stirring until homogeneous to obtain the activated wetting and dispersing agent. The hydrosilylation process involves adding 25% (by weight of PLR-1900 polyether polyol) of terminal hydrogen-based polydimethylsiloxane and stirring until homogeneous. Then, 0.1% (by weight of PLR-1900 polyether polyol) of Karstedt catalyst is added at a controlled dropping rate of 0.02 parts / min. The mixture is heated to 90°C and reacted for 6 hours to obtain the addition wetting and dispersing agent. Purification involves distilling the addition wetting and dispersing agent under reduced pressure (80°C, 6 kPa) for 1 hour to obtain the modified wetting and dispersing agent.

[0042] The preparation method of the low-foaming glass substrate cleaning solution in this application embodiment includes first preparing alkyl-blocked xylene and polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent, respectively; stirring alkyl-blocked xylene, propylene glycol methyl ether acetate, n-butanol and ethanol at room temperature and pressure for 12 minutes and mixing them evenly; then adding polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent and corrosion inhibitor, stirring for 18 minutes until completely dissolved; and finally filtering through a filter membrane to obtain the finished low-foaming glass substrate cleaning solution.

[0043] Comparative Example 1 The difference between Comparative Example 1 and Example 3 is that the xylene in Comparative Example 1 was not alkyl-blocked.

[0044] Comparative Example 2 The difference between Comparative Example 2 and Example 3 is that the wetting and dispersing agent in Comparative Example 2 is PLR-1900 wetting and dispersing agent.

[0045] Comparative Example 3 The difference between Comparative Example 3 and Example 3 is that the HZSM-5 molecular sieve in Comparative Example 3 was not modified.

[0046] Performance testing: 1. Low-foaming performance test: Referring to GB / T13173-2008 "Test Methods for Surfactants and Detergents", a Roche foam analyzer was used. The corresponding examples and comparative examples were diluted to a mass fraction of 0.5% at 25℃. The initial foam height (mL) and the foam height (mL) after 5 minutes were measured. The lower the foam height and the faster the decay, the better the low-foaming performance. Ultrasonic cleaning with a power of 200W and a frequency of 40kHz was used, and the foam overflow within 30 minutes was observed. If there was no foam overflow, it was qualified. 2. Surface tension test: Referring to GB / T22237-2008 "Determination of surface tension of surfactants", the surface tension of the sample was measured at 25℃ using the ring method. 3. Cleaning efficiency test: Select a glass substrate with photoresist residue and grease, and clean it with ultrasonic power of 200W and frequency of 40kHz for 10 minutes. Observe the residue on the substrate surface with an optical microscope and calculate the photoresist residue dissolution rate = (residual area before cleaning - residual area after cleaning) / residual area before cleaning × 100%. If there are no watermarks or oil spots, it is qualified. 4. Adsorption rate test: Immerse the cleaned glass substrate in simulated sewage containing 0.1% oil for 5 minutes, remove it and dry it. Weigh the change in mass of the substrate before and after cleaning and after immersion. Calculate the re-adsorption rate = (mass after immersion - mass after cleaning) / (mass before cleaning - mass after cleaning) × 100%. The lower the value, the better the anti-re-adhesion performance.

[0047] The performance test results are shown in Table 1 below.

[0048] Table 1 Performance Test Results

[0049] As shown in Table 1 above, in Comparative Example 1, because the toluene was not alkyl-blocked, it had strong molecular polarity and high surface tension, which significantly increased the foaming tendency. The initial foam height and the foam height after 5 minutes were much higher than those in Example 3, and foam overflow occurred during ultrasonic cleaning. Comparative Example 2 used pure PLR-1900 wetting and dispersing agent, which lacked the defoaming effect of siloxane segments and was difficult to effectively destroy the foam liquid film. It had weak low-foaming performance and insufficient wetting and suspension capabilities, resulting in watermarks and slight oil spots after cleaning. The re-adsorption rate of pollutants was high, and the re-adsorption rate of pollutants decreased significantly. Comparative Example 3 used unmodified HZSM-5 molecular sieve, which resulted in insufficient catalytic selectivity. As a result, the surface tension and low-foaming performance were slightly lower than those in Example 3. In addition, the purity of the prepared alkyl-blocked xylene was low and the dissolution stability was insufficient, resulting in a slightly lower photoresist residue dissolution rate and anti-re-adhesion performance than those in Example 3. Meanwhile, the acid strength and pore structure of HZSM-5 molecular sieves were not optimized, resulting in poor catalytic selectivity and consequently an increase in byproducts.

[0050] In summary, this application provides a low-foaming glass substrate cleaning solution. This solution prepares alkyl-blocked xylene via a self-disproportionation reaction catalyzed by HZSM-5 molecular sieves, thereby blocking the active sites of the benzene ring with alkyl groups to reduce surface tension and foaming rate. Furthermore, the siloxane segments of the polydimethylsiloxane graft / PLR-1900 wetting and dispersing agent rapidly spread at the gas-liquid interface, disrupting the stability of the foam liquid film. This, combined with the alkyl-blocked xylene, effectively prevents foam overflow and contaminant carryover. Simultaneously, the alkyl-blocked xylene provides strong dissolving power, efficiently dissolving oily contaminants such as photoresist residue and grease on the glass substrate surface. The polydimethylsiloxane graft / PLR-1900 wetting and dispersing agent significantly improves the wettability of the cleaning solution, allowing it to spread rapidly on the substrate surface while stably suspending the dissolved contaminants, preventing re-adhesion. This achieves dual-effect removal of both polar and non-polar contaminants, leaving no watermarks or oil spots after cleaning. To achieve environmental protection goals, the modified HZSM-5 molecular sieve obtained through acid leaching optimizes acid strength and pore structure, and enhances catalytic selectivity. Furthermore, the xylene self-disproportionation reaction is simple, the raw materials are controllable, and the process is concise and environmentally friendly, thereby significantly reducing production costs.

[0051] The terms “first,” “second,” “third,” “fourth,” etc., used in this application (if applicable) are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such data can be interchanged where appropriate so that the embodiments described herein can be implemented in orders other than those described herein. Furthermore, the terms “comprising” and “having,” and any variations thereof, are intended to cover non-exclusive inclusion; for example, a process, method, or apparatus that includes a series of steps or units is not necessarily limited to those explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, or apparatus.

[0052] It should be noted that the use of terms such as "first" and "second" in this application is for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include at least one of those features. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. If the combination of technical solutions is contradictory or impossible to implement, such a combination of technical solutions should be considered non-existent and not within the scope of protection claimed in this application.

[0053] This document uses specific examples to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the methods and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A low-foaming glass substrate cleaning solution, characterized in that: It comprises 25-40 parts by weight of xylene, 20-35 parts by weight of propylene glycol methyl ether acetate, 10-20 parts by weight of n-butanol, 15-25 parts by weight of ethanol, 5-10 parts by weight of wetting and dispersing agent, and 1-4 parts by weight of corrosion inhibitor; wherein the xylene is alkyl-blocked xylene; and the wetting and dispersing agent is polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent.

2. The low-foaming glass substrate cleaning solution according to claim 1, characterized in that: The preparation method of the alkyl-blocked xylene includes step ① activating HZSM-5 molecular sieve and then purging with nitrogen to obtain a clean molecular sieve; step ② preheating and vaporizing xylene under a nitrogen atmosphere, controlling the reaction temperature at 340-380℃, the pressure at 1.0-1.8MPa, and the mass hourly space velocity at 1.5-2.5h. -1 The reaction time is 3-5 hours, and the product of self-disproportionation alkyl transfer reaction is obtained after the reaction. In step ③, the product of self-disproportionation alkyl transfer reaction is condensed, distilled to obtain the fraction, dried and filtered to obtain alkyl-blocked xylene.

3. The low-foaming glass substrate cleaning solution according to claim 2, characterized in that: In step ①, the activation treatment is carried out at a controlled temperature of 530-570℃, a heating rate of 2-5℃ / min, and calcination in air atmosphere for 3.5-4.5h, followed by cooling to room temperature; the nitrogen purging is carried out at a controlled flow rate of 8-22mL / min for 25-35min; in step ②, the preheating vaporization is carried out at a controlled temperature of 150-180℃.

4. The low-foaming glass substrate cleaning solution according to claim 2, characterized in that: In step ③, the condensation is carried out at a controlled temperature of 55-75℃ to obtain a liquid material; the distillation is carried out at controlled atmospheric pressure, and the fraction with a temperature of 135-145℃ is taken as the distillate material; the drying is carried out by drying with anhydrous sodium sulfate for 2-4 hours; the filtration is carried out by filtering with a 0.22-0.45μm filter membrane to obtain alkyl-blocked xylene with a purity of ≥94%.

5. The low-foaming glass substrate cleaning solution according to claim 2, characterized in that: The HZSM-5 molecular sieve is a modified HZSM-5 molecular sieve, and the silicon-aluminum molar ratio is 50-100.

6. The low-foaming glass substrate cleaning solution according to claim 5, characterized in that: The modification method of the modified HZSM-5 molecular sieve includes pretreatment, acid leaching modification, and washing and drying. The pretreatment includes pulverizing the HZSM-5 molecular sieve to 200-300 mesh and drying it at 110-120℃ for 2-4 hours to obtain pretreated molecular sieve. The acid leaching modification involves adding 0.2-2 mol / L nitric acid solution to the pretreated molecular sieve at a solid-liquid mass ratio of 1:5-10, mixing it, stirring and refluxing it at 60-80℃ for 3-5 hours, and then filtering it to obtain modified molecular sieve. The washing and drying involves washing with deionized water until neutral and then drying it at 110-120℃ for 2-4 hours.

7. The low-foaming glass substrate cleaning solution according to claim 1, characterized in that: The preparation method of the polydimethylsiloxane graft / PLR-1900 wetting and dispersing agent includes end-group activation, hydrosilylation, and purification of PLR-1900 polyether polyol to obtain a modified wetting and dispersing agent with a grafting rate greater than 85%; the hydrosilylation includes adding 10-25% of terminal hydrogen-based polydimethylsiloxane by mass of PLR-1900 polyether polyol and stirring evenly, then adding 0.05-0.1% of Karstedt catalyst by mass of PLR-1900 polyether polyol at a controlled dropping rate of 0.01-0.02 parts / min, and reacting at 80-90℃ for 6-8 hours to obtain the addition wetting and dispersing agent.

8. The low-foaming glass substrate cleaning solution according to claim 7, characterized in that: The end-group activation includes mixing PLR-1900 polyether polyol with anhydrous isopropanol at a mass ratio of 1.6-1.8:1, heating to 60-70°C, controlling the vacuum degree to -0.08 to -0.09 MPa for dehydration for 0.8-1.2 hours, then adding 0.1-0.3% of p-hydroxyanisole by mass of PLR-1900 polyether polyol, and stirring evenly to obtain an activated wetting and dispersing agent.

9. The low-foaming glass substrate cleaning solution according to claim 7, characterized in that: The purification process involves distilling the addition wetting and dispersing agent under reduced pressure at a controlled temperature of 70-80℃ and a pressure of 4-6 kPa for 1-1.5 hours to obtain the modified wetting and dispersing agent.

10. The low-foaming glass substrate cleaning solution according to claim 7, characterized in that, The preparation method includes preparing alkyl-blocked xylene and polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent separately. Then, alkyl-blocked xylene, propylene glycol methyl ether acetate, n-butanol and ethanol are stirred at room temperature and pressure for 8-12 minutes and mixed evenly. Then, polydimethylsiloxane grafted / PLR-1900 wetting and dispersing agent and corrosion inhibitor are added and stirred for 12-18 minutes until completely dissolved. Finally, the solution is filtered through a filter membrane to obtain the finished low-foaming glass substrate cleaning solution.

Images