A high concentration inorganic developer and preparation method thereof

Abstract

The present invention proposes a high-concentration inorganic developer, which includes 5%-20% inorganic base, 7%-40% nonionic surfactant A and 1%-30% nonionic surfactant B, and the rest is high-purity water, wherein the nonionic surfactant A is a polymer containing polyoxyethylene groups and aryl ethers, and the nonionic surfactant B is an isomeric alcohol nonionic surfactant. The present invention forms a stable developer stock solution system through the combination of two nonionic surfactants, which has strong stability in a sealed state and does not stratify; moreover, when the developer is diluted 100-500 times for use, there is no residue in the development, the image is clear, and the development speed is fast.

Description

Technical Field

[0001] The present invention relates to the technical field of developer solution, and in particular to a high-concentration inorganic developer solution and a preparation method thereof. Background Art

[0002] Thin-film transistor liquid crystal display (TFT-LCD) is a mainstream display product. Due to its low cost, high brightness, and low energy consumption, the product is widely used in televisions, computers, mobile phones, and automotive fields. The TFT-LCD manufacturing process mainly includes four manufacturing processes: array, color film, nucleation, and module. The array and color film are the most important links in TFT-LCD products, and they are also the links that use the most chemicals.

[0003] The photoresists used in the color film process include BM, R, G, B, PS, and OC. Except for OC glue which does not require development, the other five types all require development. Whether the development patterns of these five photoresists are clear, whether there is peeling on the lines, whether there is photoresist residue, and the sol capacity of the developer directly affect the imaging quality of the LCD. Therefore, the development process occupies an important position in TFT-LCD.

[0004] At present, the developer for color film on the market is mainly inorganic alkaline developer, which includes inorganic alkali, surfactant and deionized water. For example, the patent application publication number CN112698552A discloses a color film developer for color film R, G, B. The alkaline developer is not easy to find the phenomenon of non-ionic surfactant precipitation and stratification at low concentration. However, once a high concentration alkaline developer needs to be prepared, the hydrophobic effect of the hydrophobic group of the surfactant with water is greater than the hydrophilic effect of the hydrophilic group, so stratification and precipitation problems occur, affecting the stability of the developer and the development effect. Summary of the invention

[0005] In view of this, the present invention proposes a high-concentration inorganic developer, the alkali concentration of the developer can reach 20%, and when diluted 500 times for use, there is no residue left in the development and the image is clear.

[0006] The technical solution of the present invention is implemented as follows: On the one hand, the present invention provides a high-concentration inorganic developer, which, calculated by mass percentage as 100%, comprises: 5%-20% inorganic alkali, 7%-40% non-ionic surfactant A and 1%-30% non-ionic surfactant B, and the rest is high-purity water;

[0007] The nonionic surfactant A is a polymer containing polyoxyethylene groups and aryl ethers; and the nonionic surfactant B is an isomeric alcohol nonionic surfactant.

[0008] On the basis of the above technical solution, preferably, the general structural formula of the nonionic surfactant A is:

[0009]

[0010] Wherein, R1 is an aryl group or an alkyl group, n is an integer, and 5≤n≤20.

[0011] On the basis of the above technical solution, preferably, R1 is an aromatic group.

[0012] On the basis of the above technical solution, preferably, the nonionic surfactant B is selected from one or more combinations of isomeric octacanol, isomeric decacanol, isomeric undecacanol, isomeric tridecacanol and isomeric octadecyl alcohol.

[0013] On the basis of the above technical solution, preferably, the inorganic base is selected from one or more combinations of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate.

[0014] On the basis of the above technical solution, preferably, the resistivity of the high-purity water is greater than 18 MΩ / cm.

[0015] On the basis of the above technical solution, preferably, the mass percentage of the inorganic base is 15-20%.

[0016] On the basis of the above technical solution, preferably, the mass percentage of the nonionic surfactant A is 25-40%.

[0017] On the basis of the above technical solution, preferably, the mass percentage of the nonionic surfactant B is 15-30%.

[0018] On the other hand, the present invention provides a method for preparing a high-concentration inorganic developer, which comprises first adding an inorganic base to high-purity water, stirring evenly, adding a nonionic surfactant B, stirring evenly again, adding a nonionic surfactant A, stirring at 1000-1500 rpm for 10-30 min, and finally filtering through an ultrafiltration membrane to obtain a developer.

[0019] A high-concentration inorganic developer and a preparation method thereof of the present invention have the following beneficial effects compared with the prior art: a stable developer stock solution system is formed by combining two non-ionic surfactants, and the developer has strong stability in a sealed state and does not delaminate; moreover, when the developer is diluted 100-500 times for use, there is no residue left after development, the image is clear, and development can be completed in 1 minute. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0021] Figure 1 This is a development diagram of Example 7 of the present invention;

[0022] Figure 2 This is the development diagram of Comparative Example 3 of the present invention. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] The developer composition is prepared according to the mass percentage shown in Table 1 below, ADD-A represents nonionic surfactant A, ADD-B represents nonionic surfactant B, wherein R1 of ADD-A in Examples 1, 4 and 6 is an aromatic group, wherein R1 of ADD-A in Examples 2, 3, 5 and 7 is an alkyl group, as shown in Table 1. In the developer preparation process, high-purity water with a resistivity greater than 18MΩ / cm is first added to the reactor, and then an appropriate amount of inorganic alkali is added, stirred at room temperature, and after stirring evenly, nonionic surfactant B is added, and nonionic surfactant A is added after stirring evenly again, and stirred at 1200rpm for 30min, and finally filtered through an ultrafiltration membrane to obtain a developer. The surfactant in Comparative Example 3 is a surfactant with patent number CN112698552A, and the amount used is 20% of the total mass of the developer. Comparative Examples 1-2 are turbid at room temperature (20-30°C), and the turbidity point cannot be determined.

[0025] Table 1 Comparison of developer solutions in Examples and Comparative Examples

[0026]

[0027] As can be seen from Table 1, Comparative Example 1 is a low-concentration developer solution, and Comparative Example 2 is a high-concentration developer solution without ADD-B. The system cannot maintain a solution state and appears milky white. After being placed for more than 30 minutes, the emulsion is stratified. Compared with Examples 2 and 5, with the same content of inorganic base and ADD-A, the higher the ADD-B content, the higher the turbidity point.

[0028] In order to evaluate the development performance of the above-mentioned embodiments and comparative examples, the following development performance test was conducted. The experimental steps are as follows: the experimental piece used is a glass substrate of 10cm×10cm. Because BM photoresist is relatively harsh for the production line to develop, BM photoresist is selected for development test with a thickness of 1.5μm. First, soak the glass substrate with glass cleaning agent, then wash and dry it with ultrapure water. Place the dry glass substrate on a spin coater, spin-coat the photoresist at a speed of 330rpm, then use a vacuum drying oven to extract most of the solvent from the substrate, cure it on a hot plate at 100°C for 85s, place the substrate at room temperature for exposure by an exposure machine, transfer the mask pattern to the substrate through exposure, and place the exposed substrate in a plug for standby use.

[0029] The developer stock solutions of Examples 1 and 7 and Comparative Examples 1-3 were diluted 100-500 times to an inorganic alkali concentration of 0.043% for later use; the developing temperature was 23° C., and the developer was sprayed onto the substrate coated with BM photoresist at a certain pressure for 85 seconds, then rinsed with ultrapure water, dried with N2, and observed under an optical microscope and an electron microscope to see whether the pattern was clear, whether there were residues and burrs, whether the CD changed, and the mask line was 7 μm. At the same time, a fixed mass of developer was developed, and the same thickness of 1.5 μm BM photoresist was developed each time, and the photoresist film break time (BP) was recorded and compared. The results are shown in Table 2.

[0030] Table 2 Comparison of the development conditions of the developer solutions of the embodiments and comparative examples

[0031] stability BM photoresist development BP(s) CD(μm) Example 1 Uniform The picture is clear, no rough edges, no residue 55 7.23 Example 2 Uniform The picture is clear, no rough edges, no residue 52 7.23 Example 5 Uniform The picture is clear, no rough edges, no residue 50 7.23 Example 7 Uniform The picture is clear, no rough edges, no residue 51 7.23 Comparative Example 1 turbid - - - Comparative Example 2 turbid - - - Comparative Example 3 Layering There is a residue 85 none

[0032] As can be seen from Table 2, after the tests of Examples 1 and 7, the developed appearance was normal, the lines had no burrs, and there was no photoresist residue (see Figure 1 ), indicating that the developer solution after diluting the high-concentration and low-concentration developer solution by 500 times has a clear development effect, and the development speed is faster than that of Comparative Example 3, indicating that the developer solution of the present invention has the technical effect of accelerating development, and can be developed within 1 minute. The formula of Comparative Example 1-2 is an emulsion, and the development experiment cannot be carried out. Comparative Example 3 has a stratification phenomenon after dilution, and the CD value cannot be tested. There is residue during development (see Figure 2 ), and the developing speed is slower than that of Examples 1 and 7. Compared with Examples 2 and 5, with the same content of inorganic base and ADD-A, the higher the content of ADD-B, the faster the developing speed, indicating that ADD-B has the effect of accelerating the development.

[0033] From the above ratio results, if only ADD-A or ADD-B is added, the stability and development characteristics of the developer cannot meet the production line process requirements. The combination of ADD-A and ADD-B can not only ensure the stability of the high-concentration developer solution, but also meet the process requirements for development characteristics. At the same time, it will speed up the development of the developer

[0034] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A high concentration inorganic developer, characterized in that: Calculated by mass percentage as 100%, it includes: 5%-20% inorganic base, 7%-40% non-ionic surfactant A and 1%-30% non-ionic surfactant B, and the rest is high-purity water; The nonionic surfactant A is a polymer containing polyoxyethylene groups and aryl ethers; the nonionic surfactant B is an isomeric alcohol nonionic surfactant; The general structural formula of the nonionic surfactant A is: Wherein, R1 is an aryl group or an alkyl group, n is an integer, and 5≤n≤20; The nonionic surfactant B is selected from one or more combinations of isomeric octacanol, isomeric decanol, isomeric undecanol, isomeric tridecanol and isomeric octadecanol.

2. A high concentration inorganic developer according to claim 1, characterized in that: The R1 is an aryl group.

3. A high concentration inorganic developer according to claim 1, characterized in that: The inorganic base is selected from one or more combinations of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate.

4. A high concentration inorganic developer according to claim 1, characterized in that: The resistivity of the high-purity water is greater than 18 MΩ / cm.

5. A high concentration inorganic developer according to claim 1, characterized in that: The mass percentage of the inorganic base is 15-20%.

6. A high concentration inorganic developer according to claim 1, characterized in that: The mass percentage of the nonionic surfactant A is 25-40%.

7. A high concentration inorganic developer according to claim 1, characterized in that: The mass percentage of the nonionic surfactant B is 15-30%.

8. The method for preparing a high-concentration inorganic developer according to any one of claims 1 to 7, characterized in that: First, add inorganic alkali into high-purity water, stir evenly, then add non-ionic surfactant B, stir evenly again, add non-ionic surfactant A, stir at 1000-1500rpm for 10-30min, and finally filter through an ultrafiltration membrane to obtain a developer.

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