Negative photoresist developer and preparation method thereof

Abstract

The present invention discloses a negative photoresist developer and a preparation method thereof. The negative photoresist developer is primarily composed of the following raw materials in weight percentage: 0.02-0.1% KOH, 0.1%-2% nonionic surfactant, and the balance water; the nonionic surfactant is a mixture of alcohols and amine aromatic polymers; the amine aromatic polymer has the following structural formula: wherein R1 is hydrogen and one of an alkyl group with a carbon chain of 3-16; R2 is hydrogen and one of an alkyl group with a carbon chain of 3-16; n is 1, 2, or 3; m is an integer between 7-16; and X is one of -O-. The developer of the present invention can reduce metal impurities and achieve finer development specifications.

Description

Technical Field

[0001] The present invention relates to the technical field of developer solutions, and in particular to a negative photoresist developer solution and a preparation method thereof. Background Art

[0002] Thin-film transistor liquid crystal displays (TFT-LCDs) are the mainstream of display technology. The entire industry can be divided into upstream basic materials, midstream panel manufacturing, and downstream end products. Upstream basic materials include glass substrates, color filters, polarizers, liquid crystals, and targets; midstream panel manufacturing includes arrays, cells, and modules; and downstream end products include televisions, computers, mobile phones, and other consumer electronics.

[0003] Color film, an upstream material, is a key component in the colorful display of LCD screens. It is a negative photoresist. The development order is BM, R, G, B, and PS, and all five types of photoresist typically use the same developer. The most commonly used developer for negative photoresists currently contains 0.02%-0.07% KOH, 0.1%-0.4% surfactant, and the balance is water.

[0004] Chinese patent application publication number CN106527065A discloses a photoresist developer comprising water, a nonionic surfactant, and an inorganic base. The nonionic surfactant comprises castor oil polyoxyethylene ether and an alicyclic substance. The resulting developer exhibits a gentler development speed and a wider range of applications. Chinese patent application publication number CN108594606A provides a developer comprising 3% by weight KOH, 5% by weight Na₂SiO₃, 20% by weight AEO₆, and the balance water. The developer exhibits a wide display range, a large operable window, excellent development results, and high development accuracy. However, with increasing demands for higher imaging resolution and image quality saturation in end products, existing developers struggle to effectively remove metal ion impurities from color film, which in turn affects development accuracy. The panel industry urgently needs to provide CF substrates with finer lines and cleaner surfaces. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a developer which can reduce the metal ions on the surface of the color film and has better precision and a high production line yield.

[0006] The present invention solves the above technical problems through the following technical means:

[0007] A negative photoresist developer is mainly composed of the following raw materials in percentage by weight: 0.02-0.1% KOH, 0.1%-2% nonionic surfactant, and the balance water; wherein the nonionic surfactant is a mixture of alcohols and amine aromatic polymers; the amine aromatic polymer has the following structural formula:

[0008]

[0009] wherein R1 is one of hydrogen and an alkyl group with a carbon chain of 3-16; R2 is one of hydrogen and an alkyl group with a carbon chain of 3-16; n is 1, 2 or 3; m is an integer between 7 and 16; X is -O-, One of them.

[0010] Beneficial effects: This invention specifically adds amine aromatic polymers and alcohol substances for compounding. The resulting formula can effectively reduce the metal ion content in the system, improve the development effect, and enhance the development accuracy. The main mechanism of action comes from the non-ionic polymer, which effectively dissolves the developed color film and adsorbs metal ions to form a complex.

[0011] Preferably, the mass of the alcohol is less than the mass of the amine aromatic polymer.

[0012] Preferably, the alcohol is a mixture of one or more of ethanol, propanol and isopropanol.

[0013] Preferably, in the structural formula of the amine aromatic polymer, R1 is hydrogen; R2 is n-octyl; n is 1; X is -O- or

[0014] Preferably, the structural formula of the amine aromatic polymer is One of them.

[0015] Preferably, the preparation process of the amine aromatic polymer comprises the following steps:

[0016] S1. Add KOH aqueous solution to the reaction apparatus, add p-chlorophenol, one of 4-chlorobenzoic acid and octylamine, and stir at 85-90° C. for 1-2 hours to obtain material A;

[0017] S2. Using NaHCO3 to adjust the mixed solvent of dioxane and water to alkaline, add material A and di-tert-butyl dicarbonate, and add ethylene oxide to carry out a ring-opening reaction to obtain material B with a boc group;

[0018] S3. Add HCl to the material B with the boc group in S2 to remove the boc group, and use a spot plate to confirm that the boc has been removed to obtain the amine aromatic polymer.

[0019] Preferably, in S1, the mass ratio of p-chlorophenol to octylamine is 1:1; the mass ratio of 4-chlorobenzoic acid to octylamine is 157:130.

[0020] Preferably, in S2, the molar ratio of the material A to ethylene oxide is 1:7-16.

[0021] Preferably, in the mixed solvent of dioxane and water, the volume ratio of dioxane to water is 1:1.

[0022] The present invention also provides a method for preparing the negative photoresist developer, comprising the following steps:

[0023] S1, adding water into the reaction apparatus at normal temperature and pressure;

[0024] S2. Turn on the cooling system to ensure that the water temperature is below 25°C, stir at a speed of 100-200 rpm, add KOH, amine aromatic polymer, and alcohol, and stir for more than 30 minutes to ensure the system is uniform;

[0025] S3. After mixing, filter through 0.3 μm, 0.2 μm and 0.1 μm filters respectively to remove impurities and obtain the negative photoresist developer.

[0026] The advantages of the present invention are: the invention specifically adds amine aromatic polymers and alcohol substances for compounding, and the resulting formula can effectively reduce the metal ion content in the system, improve the development effect, and enhance the development accuracy. The main mechanism of action comes from the non-ionic polymer, which effectively dissolves the developed color film and adsorbs metal ions to form a complex.

[0027] The developer of the present invention is a developer that can reduce metal impurities and has finer development specifications. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The BM glue line after development with the developer in Example 1 of the present invention;

[0029] Figure 2 This is the BM glue line after development with the developer in Example 2 of the present invention;

[0030] Figure 3 This is the BM glue line after development with the developer in Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0031] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, 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. 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 making creative efforts shall fall within the scope of protection of the present invention.

[0032] Unless otherwise specified, the test materials and reagents used in the following examples can be obtained from commercial sources.

[0033] If no specific techniques or conditions are specified in the examples, they can be carried out according to the techniques or conditions described in the literature in the field or according to the product instructions.

[0034] The preparation process of octylaminophenol polyoxyethylene ether described in the examples of the present invention and the comparative examples comprises the following steps:

[0035] S1. Add 150 g of 2% KOH aqueous solution into a 500 ml round-bottom flask, add 130 g of p-chlorophenol and 130 g of octylamine, and stir at 90° C. for 1 h to obtain yellow-white solid octylaminophenol. The reaction is complete with a yield of 70% and a weight of 180 g.

[0036] S2. Using NaHCO3, the pH of the mixed solvent of dioxane and water is adjusted to 9, wherein the volume ratio of dioxane to water in the mixed solvent of dioxane and water is 1:1, 180g of octylaminophenol and 155g of di-tert-butyl dicarbonate are added, and ethylene oxide is added to carry out a ring-opening reaction to obtain octylaminophenol polyoxyethylene ether with a boc group; (the EO chain length is controlled according to the amount of ethylene oxide added);

[0037] S3, adding HCl to the octylaminophenol polyoxyethylene ether with a boc group in S2 to remove the boc group, and using a dot plate to confirm that the boc has been removed to generate an amine aromatic polymer octylaminophenol polyoxyethylene ether, whose structural formula is

[0038] Among them, in Examples 1, 3 and Comparative Examples 1, 3, the molar ratio of octylaminophenol to the added ethylene oxide is 1:15, that is, m in the structural formula is 15; the structural formula of the obtained octylaminophenol polyoxyethylene ether is X is O;

[0039] In Example 2, the molar ratio of octylaminophenol to the added ethylene oxide is 1:7, and m is 7 in the structural formula of the obtained octylaminophenol polyoxyethylene ether.

[0040] In Example 4-6, the molar ratio of octylaminophenol to the added ethylene oxide is 1:10, and m is 10 in the structural formula of the obtained octylaminophenol polyoxyethylene ether.

[0041] The above is only one synthesis method, wherein the amount of reactants can be adjusted according to needs.

[0042] Example 1

[0043] A negative photoresist developer is composed of the following raw materials in percentage by weight: 0.047 wt% KOH, 0.05 wt% isopropyl alcohol, 0.1 wt% octylaminophenol polyoxyethylene ether (m=15), and the remainder pure water.

[0044] A method for preparing the negative photoresist developer comprises the following steps:

[0045] S1. Add water to a stirred tank at normal temperature and pressure;

[0046] S2. Turn on the cooling system to ensure that the water temperature is 20°C, stir at a speed of 150 rpm, add KOH, amine aromatic polymer octylaminophenol polyoxyethylene ether, and isopropyl alcohol, and stir for 35 minutes to ensure the system is uniform;

[0047] S3. After mixing, filter through 0.3μm, 0.2μm and 0.1μm filters respectively to remove impurities;

[0048] S4. Test the content of finished product components through gas phase and liquid phase equipment.

[0049] Example 2

[0050] A negative photoresist developer is composed of the following raw materials in percentage by weight: 0.04 wt% KOH, 0.05 wt% isopropyl alcohol, 0.1 wt% octylaminophenol polyoxyethylene ether (m=7), and the remainder pure water.

[0051] The preparation method of the negative photoresist developer is the same as that of Example 1.

[0052] Example 3

[0053] A negative photoresist developer is composed of the following raw materials in percentage by weight: 0.02 wt% KOH, 0.04 wt% isopropyl alcohol, 0.06 wt% octylaminophenol polyoxyethylene ether (m=15), and the remainder pure water.

[0054] A method for preparing the negative photoresist developer comprises the following steps:

[0055] S1. Add water to a stirred tank at normal temperature and pressure;

[0056] S2. Turn on the cooling system to ensure that the water temperature is 23°C, stir at a speed of 100 rpm, add KOH, amine aromatic polymer octylaminophenol polyoxyethylene ether, and isopropyl alcohol, and stir for 40 minutes to ensure the system is uniform;

[0057] S3. After mixing, filter through 0.3μm, 0.2μm and 0.1μm filters respectively to remove impurities;

[0058] S4. Test the content of finished product components through gas phase and liquid phase equipment.

[0059] Example 4

[0060] A negative photoresist developer is composed of the following raw materials in weight percentage: 0.1 wt% KOH, 0.5 wt% isopropyl alcohol, 1.5 wt% octylaminophenol polyoxyethylene ether (m=10), and the remainder pure water.

[0061] A method for preparing the negative photoresist developer comprises the following steps:

[0062] S1. Add water to a stirred tank at room temperature and pressure;

[0063] S2. Turn on the cooling system to ensure that the water temperature is 25°C, stir at a speed of 200 rpm, add KOH, amine aromatic polymer octylaminophenol polyoxyethylene ether, and isopropyl alcohol, and stir for 45 minutes to ensure the system is uniform;

[0064] S3. After mixing, filter through 0.3μm, 0.2μm and 0.1μm filters respectively to remove impurities;

[0065] S4. Test the content of finished product components through gas phase and liquid phase equipment.

[0066] Example 5

[0067] A negative photoresist developer is composed of the following raw materials in weight percentage: 0.1 wt% KOH, 0.08 wt% ethanol, 0.1 wt% octylaminophenol polyoxyethylene ether (m=10), and the remainder pure water.

[0068] A method for preparing the negative photoresist developer comprises the following steps:

[0069] S1. Add water to a stirred tank at normal temperature and pressure;

[0070] S2. Turn on the cooling system to ensure that the water temperature is 20°C, stir at a speed of 150 rpm, add KOH, amine aromatic polymer octylaminophenol polyoxyethylene ether, and ethanol, and stir for 35 minutes to ensure the system is uniform;

[0071] S3. After mixing, filter through 0.3μm, 0.2μm and 0.1μm filters respectively to remove impurities;

[0072] S4. Test the content of finished product components through gas phase and liquid phase equipment.

[0073] Example 6

[0074] A negative photoresist developer is composed of the following raw materials in weight percentage: 0.06 wt% KOH, 0.06 wt% propanol, 0.09 wt% octylaminophenol polyoxyethylene ether (m=10), and the remainder pure water.

[0075] A method for preparing the negative photoresist developer comprises the following steps:

[0076] S1. Add water to a stirred tank at normal temperature and pressure;

[0077] S2. Turn on the cooling system to ensure that the water temperature is 20°C, stir at a speed of 150 rpm, add KOH, amine aromatic polymer octylaminophenol polyoxyethylene ether, and propanol, and stir for 35 minutes to ensure the system is uniform;

[0078] S3. After mixing, filter through 0.3μm, 0.2μm and 0.1μm filters respectively to remove impurities;

[0079] S4. Test the content of finished product components through gas phase and liquid phase equipment.

[0080] Example 7

[0081] A negative photoresist developer is composed of the following raw materials in percentage by weight: 0.06 wt% KOH, 0.06 wt% propanol, 0.01 wt% ethanol, 0.09 wt% propylaminophenol polyoxyethylene ether, and the remainder pure water;

[0082] Wherein, the propylaminophenol polyoxyethylene ether is prepared according to the following process:

[0083] S1. Add 150 g of 2% KOH aqueous solution into a 500 ml round-bottom flask, add 130 g of p-chlorophenol and 59 g of propylamine, and stir at 85° C. for 2 h to obtain propylaminophenol;

[0084] S2. Using NaHCO3 to adjust the pH of a mixed solvent of dioxane and water to 9, wherein the volume ratio of dioxane to water in the mixed solvent of dioxane and water is 1:1, 122 g of propylaminophenol and 155 g of di-tert-butyl dicarbonate are added, and ethylene oxide is added to carry out a ring-opening reaction to obtain propylaminophenol polyoxyethylene ether with a boc group; wherein the molar ratio of propylaminophenol to ethylene oxide is 1:7;

[0085] S3. Add HCl to the propylaminophenol polyoxyethylene ether with a boc group in S2 to remove the boc group, and use a dot plate to confirm that the boc has been removed to generate an amine aromatic polymer propylaminophenol polyoxyethylene ether.

[0086] A method for preparing the negative photoresist developer comprises the following steps:

[0087] S1. Add water to a stirred tank at normal temperature and pressure;

[0088] S2. Turn on the cooling system to ensure that the water temperature is 20°C, stir at a speed of 150 rpm, add KOH, amine aromatic polymer propylaminophenol polyoxyethylene ether, propanol and ethanol, and stir for 35 minutes to ensure the system is uniform;

[0089] S3. After mixing, filter through 0.3μm, 0.2μm and 0.1μm filters respectively to remove impurities;

[0090] S4. Test the content of finished product components through gas phase and liquid phase equipment.

[0091] Example 8

[0092] A negative photoresist developer is composed of the following raw materials in percentage by weight: 0.08 wt% KOH, 0.05 wt% isopropyl alcohol, 0.1 wt% hexadecylaminophenol polyoxyethylene ether, and the remainder pure water;

[0093] Wherein, the preparation process of the hexadecylaminophenol polyoxyethylene ether comprises the following steps:

[0094] S1. Add 150 g of a 2% KOH aqueous solution into a 500 ml round-bottom flask, add 130 g of p-chlorophenol and 243 g of hexadecylamine, and stir at 90° C. for 1 h to obtain hexadecylaminophenol;

[0095] S2. Using NaHCO3, the pH of a mixed solvent of dioxane and water is adjusted to 9, wherein the volume ratio of dioxane to water in the mixed solvent of dioxane and water is 1:1, 270 g of hexadecylaminophenol and 155 g of di-tert-butyl dicarbonate are added, and ethylene oxide is added to carry out a ring-opening reaction to obtain hexadecylaminophenol polyoxyethylene ether with a boc group; wherein the molar ratio of hexadecylaminophenol to ethylene oxide is 1:13;

[0096] S3. Add HCl to the hexadecylaminophenol polyoxyethylene ether with a boc group in S2 to remove the boc group, and use a dot plate to confirm that the boc has been removed to generate an amine aromatic polymer hexadecylaminophenol polyoxyethylene ether.

[0097] A method for preparing the negative photoresist developer comprises the following steps:

[0098] S1. Add water to a stirred tank at normal temperature and pressure;

[0099] S2. Turn on the cooling system to ensure that the water temperature is 20°C, stir at a speed of 150 rpm, add KOH, amine aromatic polymer hexadecylaminophenol polyoxyethylene ether, and isopropyl alcohol, and stir for 35 minutes to ensure the system is uniform;

[0100] S3. After mixing, filter through 0.3μm, 0.2μm and 0.1μm filters respectively to remove impurities;

[0101] S4. Test the content of finished product components through gas phase and liquid phase equipment.

[0102] Example 9

[0103] A negative photoresist developer is composed of the following raw materials in percentage by weight: 0.07 wt% KOH, 0.1 wt% isopropyl alcohol, 0.15 wt% polyoxyethylene 4-octylaminobenzoate, and the remainder pure water;

[0104] Wherein, the preparation process of the polyoxyethylene 4-octylaminobenzoate ether comprises the following steps:

[0105] S1. Add 150g of 2% KOH aqueous solution into a 500ml round-bottom flask, add 157g of 4-chlorobenzoic acid and 130g of octylamine, and stir at 90°C for 1.5h to obtain p-octylaminobenzoic acid; its structural formula is

[0106] S2. Using NaHCO3 to adjust the pH of a mixed solvent of dioxane and water to 9, wherein the volume ratio of dioxane to water in the mixed solvent of dioxane and water is 1:1, 180 g of p-octylaminobenzoic acid and 136 g of di-tert-butyl dicarbonate are added, and ethylene oxide is added to carry out a ring-opening reaction to obtain p-octylaminobenzoic acid polyoxyethylene ether with a boc group; wherein the molar ratio of p-octylaminobenzoic acid to ethylene oxide is 1:7;

[0107] S3. Add HCl to the 4-octylaminobenzoic acid polyoxyethylene ether with a boc group in S2 to remove the boc group. Use a dot plate to confirm that the boc has been removed to generate an amine aromatic polymer 4-octylaminobenzoic acid polyoxyethylene ether, whose structural formula is:

[0108] A method for preparing the negative photoresist developer comprises the following steps:

[0109] S1. Add water to a stirred tank at normal temperature and pressure;

[0110] S2. Turn on the cooling system to ensure that the water temperature is 20°C, stir at a speed of 150 rpm, add KOH, amine aromatic polymer polyoxyethylene 4-octylaminobenzoate ether, and isopropyl alcohol, and stir for 35 minutes to ensure the system is uniform;

[0111] S3. After mixing, filter through 0.3μm, 0.2μm and 0.1μm filters respectively to remove impurities;

[0112] S4. Test the content of finished product components through gas phase and liquid phase equipment.

[0113] Example 10

[0114] A negative photoresist developer is composed of the following raw materials in percentage by weight: 0.05 wt% KOH, 0.1 wt% isopropyl alcohol, 0.1 wt% ethanol, 0.3 wt% polyoxyethylene 4-octylaminobenzoate, and the remainder pure water;

[0115] Wherein, the preparation process of the polyoxyethylene 4-octylaminobenzoate ether comprises the following steps:

[0116] S1. Add 150g of 2% KOH aqueous solution into a 500ml round-bottom flask, add 157g of 4-chlorobenzoic acid and 130g of octylamine, and stir at 90°C for 1.5h to obtain p-octylaminobenzoic acid; its structural formula is

[0117] S2. Using NaHCO3 to adjust the pH of a mixed solvent of dioxane and water to 9, wherein the volume ratio of dioxane to water in the mixed solvent of dioxane and water is 1:1, 180 g of p-octylaminobenzoic acid and 136 g of di-tert-butyl dicarbonate are added, and ethylene oxide is added to carry out a ring-opening reaction to obtain p-octylaminobenzoic acid polyoxyethylene ether with a boc group; wherein the molar ratio of p-octylaminobenzoic acid to ethylene oxide is 1:13;

[0118] S3. Add HCl to the 4-octylaminobenzoic acid polyoxyethylene ether with a boc group in S2 to remove the boc group. Use a dot plate to confirm that the boc has been removed to generate an amine aromatic polymer 4-octylaminobenzoic acid polyoxyethylene ether, whose structural formula is:

[0119] A method for preparing the negative photoresist developer comprises the following steps:

[0120] S1. Add water to a stirred tank at normal temperature and pressure;

[0121] S2. Turn on the cooling system to ensure that the water temperature is 20°C, stir at a speed of 150 rpm, add KOH, amine aromatic polymer polyoxyethylene 4-octylaminobenzoate ether, isopropyl alcohol and ethanol, and stir for 35 minutes to ensure the system is uniform;

[0122] S3. After mixing, filter through 0.3μm, 0.2μm and 0.1μm filters respectively to remove impurities;

[0123] S4. Test the content of finished product components through gas phase and liquid phase equipment.

[0124] Example 11

[0125] The only difference from Example 10 is that the preparation process of polyoxyethylene 4-octylaminobenzoate comprises the following steps:

[0126] S1. Add 150g of 2% KOH aqueous solution into a 500ml round-bottom flask, add 157g of 4-chlorobenzoic acid and 130g of octylamine, and stir at 90°C for 1.5h to obtain p-octylaminobenzoic acid; its structural formula is

[0127] S2. Using NaHCO3 to adjust the pH of a mixed solvent of dioxane and water to 9, wherein the volume ratio of dioxane to water in the mixed solvent of dioxane and water is 1:1, 180 g of p-octylaminobenzoic acid and 136 g of di-tert-butyl dicarbonate are added, and ethylene oxide is added to carry out a ring-opening reaction to obtain p-octylaminobenzoic acid polyoxyethylene ether with a boc group; wherein the molar ratio of p-octylaminobenzoic acid to ethylene oxide is 1:16;

[0128] S3. Add HCl to the 4-octylaminobenzoic acid polyoxyethylene ether with a boc group in S2 to remove the boc group. Use a dot plate to confirm that the boc has been removed to generate an amine aromatic polymer 4-octylaminobenzoic acid polyoxyethylene ether, whose structural formula is:

[0129] Comparative Example 1

[0130] The difference between this comparative example and Example 1 is that it is composed of the following raw materials in weight percentage: 0.018 wt% of KOH, 0.05 wt% of isopropyl alcohol, 0.1 wt% of octylaminophenol polyoxyethylene ether (m=15), and the rest is pure water.

[0131] Comparative Example 2

[0132] The developer described in the patent publication number CN108594606A was used, and the developer was composed of the following raw materials in the following mass concentrations: KOH 3% wt, Na2SiO3 5% wt, AEO09 20%, and the balance being water.

[0133] Comparative Example 3

[0134] The difference between this comparative example and Example 1 is that it is composed of the following raw materials in weight percentage: 0.12 wt% of KOH, 0.05 wt% of isopropyl alcohol, 0.1 wt% of octylaminophenol polyoxyethylene ether (m=15), and the rest is pure water.

[0135] Comparative Example 4

[0136] The difference between this comparative example and Example 1 is that it is composed of the following raw materials in weight percentage: KOH 0.047 wt%, isopropyl alcohol 0.05 wt%, AEO09 0.1 wt%, and the rest is pure water.

[0137] The development process is as follows: a certain BM glue is sprayed, pre-baked, exposed, developed at 23°C for 60 seconds, and post-baked before observing the morphology. The developed glass slide is ultrasonicated in 20ml of ultrapure water at room temperature and pressure for 30 minutes, and then the liquid is measured by ICP-OES.

[0138] Figure 1 The BM glue line after being developed by the developer in Example 1 of the present invention; Figure 1 It can be seen that the development reaches 4.5 μm and the straightness is intact.

[0139] Figure 2 The BM glue line after being developed with the developer in Example 2 of the present invention; Figure 2 It can be seen that the image can be developed to 8.57 μm, and the straightness meets the production line requirements but does not reach the accuracy of Example 1.

[0140] Figure 3 The BM glue line after being developed with the developer in Comparative Example 2 of the present invention; Figure 3 It can be seen that the image can be developed to 8.65 μm, but the straightness is obviously poor.

[0141] Table 1 Residual metal ion content of glass slides after development

[0142]

[0143] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A negative photoresist developer, characterized by: The invention mainly comprises the following raw materials in the following weight percentages: KOH 0.02-0.1%, non-ionic surfactant 0.1%-2%, and the balance water; wherein the non-ionic surfactant is a mixture of alcohols and amine aromatic polymers; the structural formula of the amine aromatic polymer is as follows: wherein R1 is one of hydrogen and an alkyl group with a carbon chain of 3-16; R2 is one of hydrogen and an alkyl group with a carbon chain of 3-16; n is 1, 2 or 3; m is an integer between 7 and 16; X is -O-, One of the following; The mass of the alcohol is less than the mass of the amine aromatic polymer.

2. The negative photoresist developer according to claim 1, wherein: The alcohol is a mixture of one or more of ethanol, propanol and isopropanol.

3. The negative photoresist developer according to claim 1, wherein: In the structural formula of the amine aromatic polymer, R1 is hydrogen; R2 is n-octyl; n is 1; X is -O- or 4. The negative photoresist developer according to claim 1, wherein: The structural formula of the amine aromatic polymer is One of them.

5. The negative photoresist developer according to claim 3 or 4, characterized in that: The preparation process of the amine aromatic polymer comprises the following steps: S1. Add KOH aqueous solution to the reaction apparatus, add p-chlorophenol, one of 4-chlorobenzoic acid and octylamine, and stir at 85-90° C. for 1-2 hours to obtain material A; S2. Using NaHCO3 to adjust the mixed solvent of dioxane and water to alkaline, add material A and di-tert-butyl dicarbonate, and add ethylene oxide to carry out a ring-opening reaction to obtain material B with a boc group; S3. Add HCl to the material B with the boc group in S2 to remove the boc group, and use a spot plate to confirm that the boc has been removed to obtain the amine aromatic polymer.

6. The negative photoresist developer according to claim 5, wherein: In S1, the mass ratio of p-chlorophenol to octylamine is 1:1; the mass ratio of 4-chlorobenzoic acid to octylamine is 157:

130.

7. The negative photoresist developer according to claim 5, wherein: In S2, the molar ratio of the material A to ethylene oxide is 1:7-16.

8. The negative photoresist developer according to claim 5, wherein: In the mixed solvent of dioxane and water, the volume ratio of dioxane to water is 1:

1.

9. A method for preparing a negative photoresist developer according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1, adding water into the reaction apparatus at normal temperature and pressure; S2. Turn on the cooling system to ensure that the water temperature is below 25°C, stir at a speed of 100-200 rpm, add KOH, amine aromatic polymer, and alcohol, and stir for more than 30 minutes to ensure the system is uniform; S3. After mixing, filter through 0.3 μm, 0.2 μm and 0.1 μm filters respectively to remove impurities and obtain the negative photoresist developer.

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