An electrolyte composition for cleaning OLED mask

Abstract

The present invention discloses an electrolyte composition for cleaning an OLED mask, belonging to the field of wet electronic chemicals. According to the sum of mass percentages being 100%, the electrolyte composition comprises 1-15% of a strong electrolyte, 1-10% of a chelating agent, 1-5% of an organic solvent, 0.1-2% of a bisimidazoline quaternary ammonium salt corrosion inhibitor, and the remainder is water. The corrosion inhibitor used in the present invention has excellent corrosion inhibition performance, can ensure that the anode electrode is not corroded in an alkaline solution, can improve the electrical conductivity of the solution, enhance electrolytic capacity, and it has the advantages of being easy to rinse, environmentally friendly, strong wettability, excellent corrosion inhibition effect, etc., so that the obtained electrolyte composition can be used to clean the dust, particles and oil stains in the surface of the OLED mask and the evaporation hole.

Description

Technical Field

[0001] The invention belongs to the field of wet electronic chemicals, and in particular relates to an electrolyte composition used for cleaning dust, particles and oil stains on the surface of an OLED mask and in a vapor deposition hole. Background Art

[0002] OLED (Organic Light-Emitting Diode), also known as organic electric laser display, refers to the phenomenon that organic semiconductor materials and luminescent materials emit light through carrier injection and recombination under the drive of an electric field. OLED is a device that uses a multi-layer organic thin film structure to generate electroluminescence. It is simple to make and only requires a low driving voltage. It has outstanding advantages in meeting the application of flat-panel displays. At the same time, OLED displays are thinner and lighter than LCDs, have higher brightness, lower power consumption, faster response, higher clarity, better flexibility, and higher luminous efficiency, which can meet consumers' new demands for display technology.

[0003] In the OLED industry, the quality of the metal mask directly affects the quality of the product. After the initial processing of the mask, metal and other particulate matter will remain in the grid or on the surface, affecting the normal use of the mask. During the recycling process, there will be particle impurities in the mask, which will affect the accuracy and use of the mask. They must be removed before the mask is used to ensure the yield. As for the removal of these impurities, the industry mainly uses electrolysis, using the generation of hydrogen to drive the movement of the electrolytic cleaning agent, thereby flushing the mask and taking away the peeled particle impurities to achieve a cleaning effect; at the same time, the electrolysis process will release heat, and the movement of heat can also peel off metal and dust particles.

[0004] The electrolytic cleaning tank has two types of electrodes, the cathode and the anode. The mask acts as the cathode to produce hydrogen, while the anode is made of a strong alkali-resistant conductive material, such as titanium alloy. During the long-term circulation of the electrolytic cleaning agent, the anode is immersed in the electrolyte for a long time. As the immersion time increases, there is a certain risk of corrosion to the anode metal. At the same time, the exothermic phenomenon generated during the electrolysis process strengthens the corrosion effect. Therefore, while ensuring the cleaning efficiency of the electrolyte on the mask, it is also necessary to ensure that the electrolyte does not corrode the anode, so as to avoid the reduction of electrolysis efficiency caused by anode corrosion and the increase of electrolysis cost caused by frequent replacement of the anode.

[0005] Using corrosion inhibitors is an economical and effective anti-corrosion method. There are two common types of corrosion inhibitors on the market: inorganic corrosion inhibitors and organic corrosion inhibitors. Inorganic corrosion inhibitors have poor corrosion inhibition effects on anode titanium alloys, are harmful to the environment, and it is difficult to meet emission requirements; commonly used organic corrosion inhibitors, such as diisopropylamine nitrite and hexamethylenetetramine, are easily decomposed by alkali in strong alkaline solutions, making it difficult to achieve corrosion inhibition effects. Summary of the invention

[0006] In order to overcome the problem of easy corrosion of the existing anode, the present invention provides an electrolyte composition for cleaning OLED mask, which satisfies the electrolytic cleaning efficiency and the corrosion inhibition effect on the anode metal while improving the conductivity of the electrolyte by adding a specific bisimidazoline quaternary ammonium salt corrosion inhibitor. The composition can effectively clean the dust, particles and oil stains on the surface of the OLED mask and in the evaporation holes, while preventing corrosion of the anode metal, improving the electrolysis efficiency, reducing the electrolysis cost, and has the advantages of strong cleaning ability, good wettability, easy rinsing, no residue, and environmental friendliness.

[0007] To achieve the above object, the present invention adopts the following technical solution:

[0008] An electrolyte composition for cleaning an OLED mask plate, wherein the total mass percentage is 100%, the composition contains 1-15% of a strong electrolyte, 1-10% of a chelating agent, 1-5% of an organic solvent, 0.1-2% of a bisimidazoline quaternary ammonium salt corrosion inhibitor, and the balance is water.

[0009] The strong electrolyte is selected from any one or more of potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium borate, sodium metasilicate, trisodium phosphate, etc.

[0010] The chelating agent is selected from any one or more of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, gluconic acid, sodium gluconate, citric acid, nitrilotriacetic acid, trisodium nitrilotriacetate, calcium acetate, sodium pyrophosphate, disodium hydrogen phosphate, sodium polyphosphate, diethylenetriaminepentaacetic acid, pentasodium diethylenetriaminepentaacetate, hydroxyethylethylenediamine, triethylenediamine, etc.

[0011] The organic solvent is selected from any one or more of ethanol, ethylene glycol, propylene glycol, glycerol, isopropanol, isopentanol, n-butanol, cyclohexanol, benzyl alcohol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, etc.

[0012] The water is high-purity water with a resistance value greater than 18 MΩ / cm.

[0013] The chemical structural formula of the bisimidazoline quaternary ammonium salt corrosion inhibitor is as follows:

[0014] , wherein m and n are both integers of 1 to 10. The preparation method of the bisimidazoline quaternary ammonium salt corrosion inhibitor comprises the following steps:

[0015] (1) Synthesis of intermediate 1: dicarboxylic acid and ethyleneamine were added into a three-necked flask in a molar ratio of 1:1, and the temperature was raised to 160°C under nitrogen protection, and refluxed for 3 hours. The temperature was then raised to 220°C and the reaction was continued for 4 hours. After the reaction was completed, the reaction solution was distilled to a constant weight to obtain intermediate 1. The reaction flow diagram is as follows:

[0016] ;

[0017] (2) Synthesis of intermediate 2: In a three-necked flask equipped with a stirring and reflux device, the intermediate 1 obtained was mixed with formaldehyde and acetophenone in a molar ratio of 1:2:2, and the mixture was reacted at 85°C for 4 hours. After the reaction was completed, the mixture was distilled under reduced pressure to obtain intermediate 2. The reaction flow diagram is as follows:

[0018] ;

[0019] (3) Synthesis of Bis-imidazoline Quaternary Ammonium Salt Corrosion Inhibitor: The intermediate 2 and benzyl chloride were added into a three-necked flask in a molar ratio of 1:1 and mixed. After reflux reaction at 85°C for 36 hours, the solvent and low-boiling substances were removed by vacuum distillation and then recrystallized to obtain the Bis-imidazoline Quaternary Ammonium Salt Corrosion Inhibitor. The reaction flow is as follows:

[0020] .

[0021] The preparation of the electrolyte composition is to add a strong electrolyte and a chelating agent into water, stir at a speed of 200 rpm to form a uniform system, then add an organic solvent and a bisimidazoline quaternary ammonium salt corrosion inhibitor, mix evenly, and obtain a uniform, stable, clear and transparent composition.

[0022] The significant advantages of the present invention are:

[0023] The bisimidazoline quaternary ammonium salt corrosion inhibitor used in the present invention contains imidazoline and Mannich base with excellent corrosion inhibition effect at the same time, which can effectively improve the corrosion inhibition performance. The combination of imidazoline and Mannich base effectively increases the active sites that may exist in the molecular chain, so that the obtained corrosion inhibitor is easily soluble in water and has good stability. At the same time, the quaternary ammonium salt cation contained in the structure is easily adsorbed by the negatively charged metal surface, thereby effectively inhibiting the anodic reaction of the metal, so that the corrosion inhibition efficiency can be effectively improved. The presence of heteroatoms, heterocycles and unsaturated bonds in the corrosion inhibitor makes the corrosion inhibition efficiency higher; and the aromatic ring and N atom can form multiple adsorption centers with the anode metal surface, thereby forming a denser molecular film. In addition, the amino group and the benzene ring in the corrosion inhibitor can form an electron-rich conjugated system, which has a strong adsorption capacity and can effectively inhibit the corrosion of metals in alkaline solutions. Therefore, the Gemini type corrosion inhibitor provided by the present invention has no special irritating odor, good thermal stability, low toxicity, good water solubility, and is environmentally friendly, and the presence of the acetophenone group significantly improves the cleaning efficiency. The electrolytic cleaning agent system prepared using this corrosion inhibitor can effectively alleviate the corrosion of the electrolyte to the anode during the cyclic electrolysis process, reduce cost losses, and improve electrolytic cleaning efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The FTIR graph of the bisimidazoline quaternary ammonium salt corrosion inhibitor prepared in the example. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. The exemplary implementation modes of the present invention and their description are only used to explain the present invention and are not intended to limit the present invention.

[0026] The electrolyte compositions of the examples and comparative examples were prepared according to the compositions and mass percentages shown in Table 1.

[0027] Table 1

[0028]

[0029] The preparation steps of the used bisimidazoline quaternary ammonium salt corrosion inhibitor are as follows:

[0030] 1) Synthesis of intermediate 1: 0.1 mol of sebacic acid and 0.1 mol of diethylenetriamine were weighed separately, mixed and added into a three-necked flask equipped with a mechanical stirrer and a glass water separator, and 10 mL of xylene was added as a water-carrying agent. The mixture was stirred and heated to 160°C under nitrogen protection for 3 hours of amidation reaction, and then the temperature was continued to rise to 220°C for 4 hours of cyclization reaction. After the reaction was completed, it was cooled to room temperature to obtain a light yellow oily liquid intermediate 1.

[0031] 2) Synthesis of intermediate 2: The intermediate 1 obtained, acetophenone and formaldehyde were added into a three-necked flask at a molar ratio of 1:2:2, stirred and mixed, and the temperature was raised to 85°C for constant temperature reaction for 4 hours. After the reaction was completed, the intermediate 2 was obtained by vacuum distillation.

[0032] 3) Synthesis of Bisimidazole Quaternary Ammonium Salt Corrosion Inhibitor A: The intermediate 2 was dissolved in anhydrous ethanol and added to a three-necked flask with benzyl chloride in a molar ratio of 1:1. After reflux reaction at 85°C for 36 hours, the reaction solution was evaporated to remove anhydrous ethanol, and the crude product was recrystallized three times in an ice bath with an ethanol-acetone mixed solution with a volume ratio of 1:1, and vacuum dried to obtain the final product.

[0033] like Figure 1 According to the FTIR analysis of the obtained product, 1650cm -1 The stretching vibration peak of C=N is nearby, which is the characteristic absorption peak of the imidazole ring, 3062cm -1 The stretching vibration of CH on the imidazole ring indicates that the intermediate imidazoline was successfully synthesized; 1550cm -1 Nearby is the bending vibration peak of CH, 1456cm -1 Nearby is the bending vibration peak of -CH3, 2856cm -1 and 2969cm -1 is the stretching vibration peak of -CH2, 1743cm -1 The peak is the stretching vibration peak of -C=O.

[0034] According to the product 1 H NMR ( d , DMSO, 300 MHz) analysis, its chemical shift is ( d ):2.51(d,4H, -NH-CH=N);3.27(s, 2H, -C-CH2-C);3.40(s, 6H, -N=CH-CH2-);3.46(m, 4H, -NH-CH=N-);3.60(m, 20H, -CH2-CH2-N-);3.75(m, 8H, =N-CH2-CH2-);7.49(m, 24H, -CH=CH-);7.67(m, 12H, -CH=CH-);7.95(m, 16H, -C=O-CH-CH-).

[0035] According to the product 13 C NMR ( d , DMSO, 300 MHz) analysis, its chemical shift is ( d):34.7;37.6;40.4;48.7;51.5;53.8;128.8;133.1;136.7;166.60;198.6;

[0036] According to HRMS analysis of the obtained product, its molecular formula is C 54 H 60 N6O4Cl, m / z: 891.44

[0037] The above proves that the bisimidazoline quaternary ammonium salt corrosion inhibitor with n=1 and m=1 was successfully synthesized.

[0038] The electrolytic cleaning effect of the electrolyte compositions of Examples 1-5 and Comparative Examples 1-6 on the mask was evaluated by the following test. The test method is as follows:

[0039] 1. Cut the mask sheet into 1.7cm×2.0cm size to connect the cathode electrode, and the platinum titanium electrode 3cm×4cm to connect the anode electrode;

[0040] 2. Coat the mask sheet used as cathode with a certain amount of sticky PT to simulate the removal ability of macromolecular substances during electrolysis;

[0041] 3. Place the prepared mask sheet with impurities into the electrolyte and perform electrolysis at room temperature at 25°C. After the electrolysis is completed within the prescribed time, rinse the electrolyte remaining on the electrode with isopropyl alcohol and wash with pure water. Then blow dry the electrode with nitrogen and observe under a microscope:

[0042] ① Removal rate of sticky PT on the mask surface, removal rate (mass %) = [{weight of sample before cleaning (g)} - {weight of sample after cleaning (g)}] / [{weight of sample before cleaning (g)} - {weight of test piece (g)}] × 100

[0043] ② Mask Partical Residue

[0044] ③Corrosion of anode electrode.

[0045] The results are shown in Table 2.

[0046] Table 2

[0047]

[0048] It can be seen from Tables 1 and 2 that the electrolyte composition prepared by the embodiment can remove the sticky PT on the surface of the mask sheet, has an excellent cleaning effect on macromolecular substances, has a good removal effect on particulate impurities such as Partical, is easy to rinse without residue, does not corrode the anode metal electrode, can reduce the replacement frequency of the electrode, improve the electrolysis efficiency, reduce the loss, and save costs.

[0049] Compared with Example 1, in Comparative Example 1, no corrosion inhibitor was added. Although the comparative example 1 had a better removal ability for particulate impurities and sticky PT, it had a certain corrosion behavior on the metal electrode.

[0050] Compared with Example 2, Comparative Example 2 uses 1227 as a corrosion inhibitor, which has a poor cleaning effect on sticky PT and a poor ability to remove particulate impurities, and causes certain corrosion to the electrode.

[0051] Compared with Example 3, Comparative Example 3 uses oleic acid hydroxyethyl imidazoline as a corrosion inhibitor. Although the metal electrode is not corroded, it has no obvious promoting effect on the cleaning effect, and the removal of sticky PT is poor, and the removal ability of particulate impurities is also poor.

[0052] Compared with Example 4, Comparative Example 4 uses oleic acid imidazoline sulfate methylamine as a corrosion inhibitor and increases the content of the organic solvent. It does not corrode the metal electrode, but the electrolysis effect is still general and the cleaning ability for Partical is poor.

[0053] Compared with Example 5, Comparative Examples 5 and 6 use bisimidazoline diethanol borate and PMI-2-IPM as corrosion inhibitors, respectively, which do not corrode metal electrodes and have good cleaning ability for Particals, but have average removal ability for sticky PT and reduced cleaning ability.

[0054] As can be seen from the above-mentioned embodiments and comparative examples, the addition of the bisimidazoline quaternary ammonium salt corrosion inhibitor can play a certain corrosion inhibition role on the metal anode electrode and increase its service life; at the same time, it improves the cleaning ability of the sticky PT and metal particle impurities on the mask, that is, it can exert good electrolytic cleaning and corrosion inhibition ability under less addition. In addition, the addition amount of the strong electrolyte and the chelating agent also affects the electrolysis efficiency and the cleaning ability of the metal ion impurities, and the addition amount of the organic solvent has a certain influence on the stripping speed of the particle impurities. In summary, the present invention can significantly improve the corrosion inhibition performance of the electrolyte, improve the electrolysis efficiency, reduce the cost loss, improve the cleaning ability of the mask, ensure the service life, easy to rinse, and no metal residue is produced on the mask, which is environmentally friendly.

[0055] The above embodiments describe the present invention in detail, but they are only examples and do not limit the patent scope of the present invention. Any equivalent modification and substitution of the present invention using the present description is also within the scope of the present invention and is included in the patent protection scope of the present invention.

Claims

1. An electrolyte composition for cleaning an OLED mask, characterized in that: The composition contains 1-15% of a strong electrolyte, 1-10% of a chelating agent, 1-5% of an organic solvent, 0.1-2% of a bisimidazoline quaternary ammonium salt corrosion inhibitor, and the remainder is water, based on the sum of the mass percentages being 100%; The chemical structural formula of the bisimidazoline quaternary ammonium salt corrosion inhibitor is as follows: , where m and n are both integers from 1 to 10; The preparation steps of the bisimidazoline quaternary ammonium salt corrosion inhibitor are as follows: 1) Synthesis of intermediate 1: dicarboxylic acid and ethyleneamine were mixed in a molar ratio of 1:1, heated to 160°C under nitrogen protection, refluxed for 3 hours, and then continued to heat to 220°C for 4 hours. After the reaction, the reaction solution was distilled to constant weight to obtain intermediate 1; 2) Synthesis of intermediate 2: The intermediate 1 obtained was mixed with formaldehyde and benzaldehyde in a molar ratio of 1:2:2, and the mixture was reacted at 85°C for 4 hours. After the reaction, the mixture was distilled under reduced pressure to obtain intermediate 2; 3) Synthesis of a bisimidazoline quaternary ammonium salt corrosion inhibitor: The intermediate 2 obtained and benzyl chloride were mixed in a molar ratio of 1:1, and refluxed at 85° C. for 36 hours, and then the solvent and low-boiling substances were removed by vacuum distillation and recrystallization was performed to obtain the bisimidazoline quaternary ammonium salt corrosion inhibitor; Wherein, the chemical structural formula of the dicarboxylic acid is , the chemical structural formula of the ethyleneamine is .

2. The electrolyte composition for cleaning an OLED mask according to claim 1, characterized in that: The strong electrolyte is selected from any one or more of potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium borate, sodium metasilicate, and trisodium phosphate.

3. The electrolyte composition for cleaning an OLED mask according to claim 1, characterized in that: The chelating agent is selected from any one or more of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, gluconic acid, sodium gluconate, citric acid, nitrilotriacetic acid, trisodium nitrilotriacetate, calcium acetate, sodium pyrophosphate, disodium hydrogen phosphate, sodium polyphosphate, diethylenetriaminepentaacetic acid, pentasodium diethylenetriaminepentaacetate, hydroxyethylethylenediamine, and triethylenediamine.

4. The electrolyte composition for cleaning an OLED mask according to claim 1, characterized in that: The organic solvent is selected from any one or more of ethanol, ethylene glycol, propylene glycol, glycerol, isopropanol, isopentanol, n-butanol, cyclohexanol, benzyl alcohol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monobutyl ether.

5. The electrolyte composition for cleaning an OLED mask according to claim 1, characterized in that: The water is high-purity water with a resistance value greater than 18 MΩ / cm.

6. The electrolyte composition for cleaning an OLED mask according to claim 1, characterized in that: A strong electrolyte and a chelating agent are added to water, and the mixture is stirred at a speed of 200 rpm to form a uniform system. Then, an organic solvent and a bisimidazoline quaternary ammonium salt corrosion inhibitor are added, and the mixture is mixed evenly to obtain a uniform, stable, clear and transparent composition.

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