A water-in-oil double-cloud-point liquid crystal cleaning agent

Abstract

This application discloses a water-in-oil type dual-cloud-point liquid crystal cleaning agent, comprising the following raw materials in parts by weight: 50-80 parts of oil phase, 5-20 parts of surfactant, 5-10 parts of co-surfactant, and 5-30 parts of aqueous phase; wherein, the oil phase is selected from olefins and isopropyl myristate, and the olefins have 9-14 carbon atoms; the surfactants are nonionic surfactants and gemini surfactants, and the weight ratio of the nonionic surfactants to the gemini surfactants is (0.5-1.2):1; the nonionic surfactants are selected from secondary alcohol polyoxyethylene ethers and alkynyl alcohol polyoxyethylene ethers; the gemini surfactants are rosin-based anionic surfactants and lauryl alcohol polyoxyethylene ether (3) carboxylate symmetric succinate diester surfactants. The cleaning agent prepared by this application has a fast cleaning speed, excellent cleaning effect, and is biodegradable, environmentally friendly, and pollution-free.

Description

Technical Field

[0001] This application relates to the field of cleaning agents, and in particular to an oil-in-water type double-cloud-point liquid crystal cleaning agent. Background Technology

[0002] LCD is a type of display that uses liquid crystal as its material. Liquid crystal is a type of organic compound that exists in a state between liquid and solid. At room temperature, it exhibits both the fluidity of a liquid and the optical anisotropy of a crystal. When heated to a certain temperature, it becomes a transparent liquid, and when cooled, it becomes a crystalline state.

[0003] During the LCD manufacturing process, multiple cleaning processes are required to ensure product performance and lifespan. The most crucial step is cleaning the surface of the LCD cell, pins, and crevices after the liquid crystal is filled into the vacuum system, removing any residual liquid crystal. If this residual liquid crystal is not effectively removed, it will affect the product's appearance, display quality, yield rate, performance, and lifespan. Furthermore, under high temperature and humidity conditions, it may even cause electrode open circuits. Therefore, cleaning residual liquid crystal is indispensable.

[0004] Currently, non-ODS cleaning agents in the LCD industry come in three types: water-based, semi-aqueous, and solvent-based. Water-based cleaning agents are highly dependent on ultrasound, and water has a higher surface tension than solvents, resulting in poor wetting performance in narrow crevices and a slower cleaning speed. While semi-aqueous cleaning agents offer faster cleaning speeds, they have lower flash points and a higher risk factor; the rinse water after cleaning is not only difficult to rinse but also has surface oil and high COD, failing to meet environmental protection requirements.

[0005] Therefore, there is an urgent need to develop a cleaning agent that is fast, effective, and environmentally friendly. Summary of the Invention

[0006] In order to solve at least one of the above-mentioned technical problems and to develop a cleaning agent that is fast, effective and environmentally friendly, this application provides an oil-in-water type double-cloud-point liquid crystal cleaning agent.

[0007] A water-in-oil type dual-cloud-point liquid crystal cleaning agent, comprising the following raw materials in parts by weight: 50-80 parts oil phase, 5-20 parts surfactant, 5-10 parts co-surfactant and 5-30 parts water phase;

[0008] The oil phase is selected from olefins and isopropyl myristate, wherein the olefins have 9-14 carbon atoms.

[0009] The surfactant is a nonionic surfactant and a gemini surfactant, and the weight ratio of the nonionic surfactant to the gemini surfactant is (0.5-1.2):1;

[0010] The nonionic surfactant is selected from secondary alcohol polyoxyethylene ether and alkynyl alcohol polyoxyethylene ether;

[0011] The twin surfactants are rosin-based anionic surfactants and lauryl alcohol polyoxyethylene ether (3) carboxylate symmetric succinate diester surfactants.

[0012] By adopting the above technical solution, the cleaning agent prepared by this application using special components and proportions has a fast cleaning speed, excellent cleaning effect, and the prepared cleaning agent is biodegradable, environmentally friendly and pollution-free.

[0013] The oil phase of this application is selected from olefins and isopropyl myristate, which improves the wetting properties of the cleaning agent.

[0014] This application uses a compound system of nonionic surfactants and gemini surfactants to prepare a special water-in-oil microemulsion cleaning agent, forming a special double cloud point characteristic, which improves the cleaning rate of the cleaning agent. It also has a high flash point, which improves the safety performance. Furthermore, the rinsing water after cleaning can form an oil-in-water microemulsion, which is easy to rinse. There is no residual cleaning agent on the surface of the LCD box, pins and crevices, and the cleaning and rinsing effect is excellent.

[0015] The nonionic surfactant is formulated by compounding specific secondary alcohol polyoxyethylene ether and alkynyl alcohol polyoxyethylene ether to form a nonionic surfactant compound, and the cleaning agent prepared by the compound has excellent surface activity.

[0016] Gemini surfactants are formulated by combining specific rosin-based anionic surfactants and lauryl alcohol polyoxyethylene ether (3) carboxylate symmetric succinic acid diester surfactants, anionic surfactants and nonionic surfactants to form a gemini surfactant system, which greatly improves the wettability and compatibility of the cleaning agent, and has high surface activity and fast cleaning speed.

[0017] Optionally, the weight ratio of the secondary alcohol polyoxyethylene ether to the alkynyl alcohol polyoxyethylene ether is (2-3):4.

[0018] Optionally, the weight ratio of the rosin-based anionic surfactant and the lauryl alcohol polyoxyethylene ether (3) carboxylate symmetric succinate diester surfactant is 1:(0.8-1.5).

[0019] By adopting the above technical solutions, the nonionic surfactants and gemini surfactants prepared in this application using specific ratios exhibit high activity and excellent overall performance.

[0020] Optionally, the content of isopropyl myristate is 15-30 wt% of the oil phase content.

[0021] Optionally, the cleaning agent further includes modified microcrystalline cellulose, wherein the content of the modified microcrystalline cellulose is 1-5 wt% of the oil phase.

[0022] Optionally, the particle size of the modified microcrystalline cellulose is 50-200 nm.

[0023] Optionally, the modified microcrystalline cellulose comprises raw materials in the following weight ratio: microcrystalline cellulose: sunflower seed oil: ethanol = 1:(3-5):(6-8).

[0024] By adopting the above technical solution, this application also adds modified microcrystalline cellulose, which has both hydrophilic and oleophilic properties. As a porous medium, it improves the cleaning effect of the cleaning agent on liquid crystals.

[0025] Optionally, the cleaning agent further includes triethanolamine borate, wherein the content of triethanolamine borate is 2-4 wt% of the surfactant content.

[0026] By adopting the above technical solution, this application also adds triethanolamine borate ester, which produces a cleaning agent with a high flash point, good safety, high surface activity, fast cleaning speed, and high efficiency.

[0027] Optionally, the cleaning agent has two cloud points, T1 and T2, where T1 is 44-54℃ and T2 is ≥80℃.

[0028] By adopting the above technical solution, the cleaning agent prepared in this application has a double cloud point characteristic. Based on the double cloud point characteristic, the characteristics of the cleaning agent prepared in this application can be controlled, which not only improves the cleaning effect of the cleaning agent, but also makes the rinse water after cleaning easier to rinse, reduces water waste, and saves water resources.

[0029] In summary, the present invention has at least one of the following beneficial technical effects:

[0030] 1. The cleaning agent prepared using special components and proportions in this application has a fast cleaning speed, excellent cleaning effect, and is biodegradable, environmentally friendly and pollution-free.

[0031] 2. This application uses a compound system of nonionic surfactant and gemini surfactant to prepare a special water-in-oil microemulsion cleaning agent, which forms a special double cloud point characteristic, improves the cleaning rate of the cleaning agent, and has a high flash point, which improves the safety performance. Moreover, the rinsing water after cleaning can form an oil-in-water microemulsion, which is easy to rinse. There is no residual cleaning agent on the surface of the LCD box, pins and crevices, and the cleaning and rinsing effect is excellent.

[0032] 3. Gemini surfactants are formulated by combining specific anionic and nonionic surfactants to form a gemini surfactant system, which greatly improves the wettability and compatibility of the cleaning agent, and has high surface activity and fast cleaning speed. Detailed Implementation

[0033] The present application will be further described in detail below with reference to the embodiments.

[0034] A water-in-oil type dual-cloud-point liquid crystal cleaning agent, comprising the following raw materials in parts by weight: 50-80 parts oil phase, 5-20 parts surfactant, 5-10 parts co-surfactant and 5-30 parts water phase;

[0035] The oil phase is selected from olefins and isopropyl myristate, wherein the olefins have 9-14 carbon atoms.

[0036] The surfactant is a nonionic surfactant and a gemini surfactant, and the weight ratio of the nonionic surfactant to the gemini surfactant is (0.5-1.2):1;

[0037] The nonionic surfactant is selected from secondary alcohol polyoxyethylene ether and alkynyl alcohol polyoxyethylene ether;

[0038] The twin surfactants are rosin-based anionic surfactants and lauryl alcohol polyoxyethylene ether (3) carboxylate symmetric succinate diester surfactants.

[0039] One of the important processes in LCD production is filling liquid crystal into a vacuum system. However, after filling, a large amount of residual liquid crystal remains on the surface of the LCD cell, pins, and slits. This requires cleaning. However, if the residual liquid crystal cannot be effectively removed, it will affect the appearance of the product, the display effect of the LCD, the yield rate, the performance and lifespan of the product, and may even cause electrode open circuits under high temperature and high humidity conditions.

[0040] Currently, water-based cleaning agents are highly dependent on ultrasound, and water has a higher surface tension than solvents, resulting in poor wetting performance in narrow spaces and low cleaning speed. While semi-aqueous cleaning agents offer faster cleaning speeds, they have lower flash points and higher safety risks; the rinse water after cleaning is not only difficult to rinse but also has surface oil and high COD, failing to meet environmental protection requirements.

[0041] To address the above problems, the inventors of this application designed the technical solution of this application. First, the oil phase of this application is selected from olefins and isopropyl myristate, which improves the wetting performance of the cleaning agent.

[0042] Finally, a special water-in-oil microemulsion cleaning agent was prepared by using a combination system of nonionic surfactants and gemini surfactants. This process creates a unique double cloud point characteristic, which improves the cleaning rate of the cleaning agent. It also has a high flash point, which enhances its safety performance. Furthermore, the rinse water after cleaning can form an oil-in-water microemulsion, which is easy to rinse. There is no residual cleaning agent on the LCD surface, pins, and crevices, resulting in excellent cleaning and rinsing effects.

[0043] The nonionic surfactant is formulated by compounding specific secondary alcohol polyoxyethylene ether and alkynyl alcohol polyoxyethylene ether to form a nonionic surfactant compound, and the cleaning agent prepared by the compound has excellent surface activity.

[0044] Gemini surfactants are formulated by combining specific rosin-based anionic surfactants and lauryl alcohol polyoxyethylene ether (3) carboxylate symmetric succinic acid diester surfactants, anionic surfactants and nonionic surfactants to form a gemini surfactant system, which greatly improves the wettability and compatibility of the cleaning agent, and has high surface activity and fast cleaning speed.

[0045] Therefore, the cleaning agent prepared by this application using special components and proportions has a fast cleaning speed, excellent cleaning effect, and is biodegradable, environmentally friendly and pollution-free.

[0046] Cleaning method: The cleaning agent prepared in this application is used to ultrasonically clean the liquid crystal at a temperature below 45°C. After cleaning, the water temperature in the rinsing tank is controlled at 55-80°C for rinsing.

[0047] Unless otherwise specified, all raw materials used in this application are derived from commercially available sources.

[0048] Alkenes: have 9-14 carbon atoms;

[0049] Isopropyl myristate: 98% purity;

[0050] Secondary alcohol polyoxyethylene ether: purity 98%;

[0051] Acynyl alcohol polyoxyethylene ether: purity 98%;

[0052] Rosin-based anionic surfactant: 99% purity;

[0053] Lauryl alcohol polyoxyethylene ether (3) carboxylate symmetric succinate diester surfactant: purity 99%;

[0054] Butanol: 99% purity;

[0055] Microcrystalline cellulose: pharmaceutical grade;

[0056] Sunflower seed oil: Brand: Golden Dragon Fish;

[0057] Ethanol: 99% purity;

[0058] Triethanolamine borate: 99% purity.

[0059] Testing items and methods:

[0060] Liquid crystal removal rate: The cleaning effect on the product surface and slits was observed using a metallographic microscope, and the liquid crystal removal rate on the LCD cell surface, pins and slits was calculated using the area difference subtraction method.

[0061] Cloud point: The cloud point of the cleaning agent is tested according to the standard test method for cloud point of nonionic surfactants, ASTM D2024-65 (1997). Specific Implementation

[0063] Examples 1-5

[0064] A water-in-oil type double-cloud-point liquid crystal cleaning agent, the specific raw material weight parts are shown in Table 1.

[0065] Table 1. Raw material weight parts for Examples 1-5

[0066]

[0067] The co-surfactant is butanol, and the aqueous phase is deionized water.

[0068] The surfactants are nonionic surfactants and gemini surfactants, and the weight ratio of nonionic surfactants to gemini surfactants is shown in Table 2.

[0069] Table 2 Weight ratio of nonionic surfactants and gemini surfactants

[0070]

[0071] The nonionic surfactants are secondary alcohol polyoxyethylene ether and alkynyl alcohol polyoxyethylene ether, and the weight ratio of secondary alcohol polyoxyethylene ether and alkynyl alcohol polyoxyethylene ether is shown in Table 3.

[0072] Table 3 Weight ratio of secondary alcohol polyoxyethylene ether and alkynyl alcohol polyoxyethylene ether

[0073]

[0074] The twin surfactants are rosin-based anionic surfactants and lauryl polyoxyethylene ether (3) carboxylate symmetrical succinate diester surfactants. The weight ratio of rosin-based anionic surfactants and lauryl polyoxyethylene ether (3) carboxylate symmetrical succinate diester surfactants is shown in Table 4.

[0075] Table 4 Gemini Surfactant Ratio

[0076]

[0077] Example 1

[0078] The content of isopropyl myristate is 15 wt% of the oil phase content, and the number of carbon atoms in the olefin is 9.

[0079] Example 2

[0080] The content of isopropyl myristate is 18 wt% of the oil phase content, and the number of carbon atoms in the olefin is 11.

[0081] Example 3

[0082] The content of isopropyl myristate is 21 wt% of the oil phase content, and the number of carbon atoms in the olefin is 14.

[0083] Example 4

[0084] The content of isopropyl myristate is 25 wt% of the oil phase content, and the number of carbon atoms in the olefin is 10.

[0085] Example 5

[0086] The content of isopropyl myristate is 30 wt% of the oil phase content, and the number of carbon atoms in the olefin is 12.

[0087] Comparative Examples 1-4

[0088] Comparative Example 1

[0089] Based on Example 3, except that the content of isopropyl myristate is 0, an equal amount of deionized water is used to replace isopropyl myristate, and the other components and preparation methods are the same as in Example 3.

[0090] Comparative Example 2

[0091] Based on Example 3, except that the surfactants are all nonionic surfactants, the other components and preparation methods are the same as in Example 3.

[0092] Comparative Example 3

[0093] Based on Example 3, except that the surfactants are all gemini surfactants, the other components and preparation methods are the same as in Example 3.

[0094] Comparative Example 4

[0095] Based on Example 3, except that the Gemini surfactants are all rosin-based anionic surfactants, the other components and preparation methods are the same as in Example 3.

[0096] The cloud point of the cleaning agents prepared in Examples 1-5 and Comparative Examples 1-4 was tested, and the cleaning agents were used to clean the residual liquid crystal on the LCD cell. The removal rate of the residual liquid crystal on the LCD cell was tested, and the test results are shown in Table 5.

[0097] Table 5. Test results of Examples 1-5

[0098]

[0099] As can be seen from Examples 1-5, Comparative Examples 1-4 and Table 5, the cleaning agent prepared in this application removes residual liquid crystal on the LCD cell with good cleaning effect. The liquid crystal removal rate on the LCD surface and pins is as low as 99.89%, and the liquid crystal removal rate in the slits is as low as 99.86%. The cleaning speed is fast, with a maximum cleaning time of 5 minutes. The cloud point T1 is 44-54℃, and the cloud point T2 is ≥80℃. Based on the dual cloud point characteristics of the prepared cleaning agent, the microemulsion state of the cleaning agent is controlled during cleaning. When cleaning residual liquid crystal, the oil-in-water state is maintained, which improves the cleaning rate. After cleaning, when rinsing the LCD cell, the state is controlled to be oil-in-water, which makes the rinsing water easy to rinse clean and reduces the amount of water used.

[0100] As can be seen from Comparative Example 1 and Table 5, the oil phase of this application does not contain isopropyl myristate, which reduces the wettability of the cleaning agent prepared in this application, resulting in poor liquid crystal removal and a smaller cloud point than in Example 3.

[0101] As can be seen from Comparative Examples 2-3 and Table 5, the present application uses nonionic surfactants and gemini surfactants to prepare a surfactant compound system. The prepared cleaning agent has excellent liquid crystal removal effect, fast cleaning speed, and can form a dual-cloud point system.

[0102] As can be seen from Comparative Example 4 and Table 5, the Gemini surfactant prepared by the combination of anionic and nonionic surfactants in this application has excellent liquid crystal removal effect, fast cleaning speed and can form a double cloud point system.

[0103] Examples 6-10

[0104] Example 6

[0105] Based on Example 3, except that modified microcrystalline cellulose with a content of 1 wt% of the oil phase and a particle size of 80 nm is added, the other components and preparation methods are the same as in Example 3.

[0106] Example 7

[0107] Based on Example 3, except that modified microcrystalline cellulose with a content of 4 wt% of the oil phase and a particle size of 200 nm is added, the other components and preparation methods are the same as in Example 3.

[0108] Example 8

[0109] Based on Example 3, except that modified microcrystalline cellulose with a content of 5 wt% of the oil phase and a particle size of 100 nm is added, the other components and preparation methods are the same as in Example 3.

[0110] Example 9

[0111] Based on Example 3, except that modified microcrystalline cellulose with a content of 3 wt% of the oil phase and a particle size of 150 nm is added, the other components and preparation methods are the same as in Example 3.

[0112] Example 10

[0113] Based on Example 3, except that 2 wt% of modified microcrystalline cellulose was added to the oil phase and the particle size of the modified microcrystalline cellulose was 50 nm, the other components and preparation methods were the same as in Example 3.

[0114] The specific raw material composition of the modified microcrystalline cellulose is shown in Table 6.

[0115] Table 6 Specific Raw Material Components of Modified Microcrystalline Cellulose

[0116] raw material components Example 6 Example 7 Example 8 Example 9 Example 10 microcrystalline cellulose / kg 1 1 1 1 1 Sunflower seed oil / kg 3.5 3 4 5 4.5 ethanol / kg 6 7 7.5 8 6.5

[0117] The modified microcrystalline cellulose is prepared by mixing and stirring microcrystalline cellulose, sunflower seed oil and ethanol evenly.

[0118] The cleaning agents prepared in Examples 6-10 were used to clean the residual liquid crystal on the LCD cell, and the removal rate of the residual liquid crystal on the LCD cell was tested. The test results are shown in Table 7.

[0119] Table 7. Test results of the cleaning agents prepared in Examples 6-10

[0120]

[0121]

[0122] As can be seen from Examples 6-10 and Table 7, the cleaning agent prepared by adding modified microcrystalline cellulose in this application has excellent cleaning effect, with a slit liquid crystal removal rate of 99.995% and a fast cleaning speed of up to 4 minutes. The inventors speculate that modified microcrystalline cellulose, as a porous medium, improves the dispersibility of the aqueous and oil phases, thereby making the liquid crystal dissolve more fully and the cleaning effect better when cleaning the liquid crystal residue on the surface of the LCD cell and the pins.

[0123] Examples 11-15

[0124] Example 11

[0125] Based on Example 6, except that the content of triethanolamine borate ester is 2 wt% of the surfactant content, the other components and preparation methods are the same as in Example 6.

[0126] Example 12

[0127] Based on Example 6, except that the content of triethanolamine borate ester is 2.5 wt% of the surfactant content, the other components and preparation methods are the same as in Example 6.

[0128] Example 13

[0129] Based on Example 6, except that the content of triethanolamine borate ester is 3 wt% of the surfactant content, the other components and preparation methods are the same as in Example 6.

[0130] Example 14

[0131] Based on Example 6, except that the content of triethanolamine borate ester is 3.5 wt% of the surfactant content, the other components and preparation methods are the same as in Example 6.

[0132] Example 15

[0133] Based on Example 6, except that the content of triethanolamine borate ester is 4 wt% of the surfactant content, the other components and preparation methods are the same as in Example 6.

[0134] The cleaning agents prepared in Examples 11-15 were used to clean the residual liquid crystal on the LCD cell, and the removal rate of the residual liquid crystal on the LCD cell was tested. The test results are shown in Table 8.

[0135] Table 8. Test results of the cleaning agents prepared in Examples 11-15

[0136]

[0137]

[0138] As can be seen from Examples 11-15 and Table 8, the cleaning agent prepared by adding triethanolamine borate in this application can achieve a surface liquid crystal removal rate of 100% and a slit liquid crystal removal rate of 99.999%, demonstrating excellent cleaning effect.

[0139] The above are all preferred embodiments of this application, and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the principles of this application should be covered within the scope of protection of this application.

Claims

1. A water-in-oil type dual-cloud-point liquid crystal cleaning agent, characterized in that, The raw materials include the following parts by weight: 50-80 parts oil phase, 5-20 parts surfactant, 5-10 parts co-surfactant and 5-30 parts aqueous phase; The oil phase is a mixture of olefins and isopropyl myristate, wherein the olefins have 9-14 carbon atoms. The surfactant is a mixture of nonionic surfactant and gemini surfactant, wherein the weight ratio of nonionic surfactant to gemini surfactant is (0.5-1.2):1; The nonionic surfactant is a mixture of secondary alcohol polyoxyethylene ether and alkynyl alcohol polyoxyethylene ether; The Gemini surfactant is a mixture of rosin-based anionic surfactant and lauryl alcohol polyoxyethylene ether (3) carboxylate symmetric succinate diester surfactant; The weight ratio of the secondary alcohol polyoxyethylene ether to the alkynyl alcohol polyoxyethylene ether is (2-3):4; The weight ratio of the rosin-based anionic surfactant to the lauryl alcohol polyoxyethylene ether (3) carboxylate symmetric succinate diester surfactant is 1:(0.8-1.5). The cleaning agent has two cloud points, T1 and T2, where T1 is 44-54℃ and T2 is ≥80℃.

2. The water-in-oil type dual-cloud-point liquid crystal cleaning agent according to claim 1, characterized in that, The content of isopropyl myristate is 15-30 wt% of the oil phase content.

3. The water-in-oil type dual-cloud-point liquid crystal cleaning agent according to claim 1, characterized in that, The cleaning agent also includes modified microcrystalline cellulose, the content of which is 1-5 wt% of the oil phase.

4. The water-in-oil type dual-cloud-point liquid crystal cleaning agent according to claim 3, characterized in that, The modified microcrystalline cellulose has a particle size of 50-200 nm.

5. The water-in-oil type dual-cloud-point liquid crystal cleaning agent according to claim 3, characterized in that, The modified microcrystalline cellulose comprises the following raw materials in the following weight ratio: microcrystalline cellulose: sunflower seed oil: ethanol = 1: (3-5): (6-8).

6. The water-in-oil type dual-cloud-point liquid crystal cleaning agent according to claim 1, characterized in that, The cleaning agent also includes triethanolamine borate, the content of which is 2-4 wt% of the surfactant content.

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