Preparation method and application of hydrophilic stripping solution

Abstract

The present invention relates to the technical field of stripping liquid compositions, and in particular to a preparation method and application of a hydrophilic stripping liquid. The aqueous stripping liquid is composed of a water-soluble organic solvent, a surfactant, a corrosion inhibitor, a dispersant, an organic amine mixture, a penetrant, a protective agent, and deionized water. The aqueous stripping liquid designed by the present invention is modified by treating the above-mentioned surfactant, dispersant, and penetrant, and the obtained aqueous stripping liquid has good effect and high permeability. There is basically no residue on the surface of the substrate after cleaning, and basically no toxic and harmful substances are involved in the production process. The product has no corrosion hazard to the substrate and is suitable for industrial promotion.

Description

Technical Field

[0001] The invention relates to the technical field of stripping liquid compositions, and in particular to a preparation method and application of a hydrophilic stripping liquid. Background Art

[0002] The production technology of semiconductor elements or liquid crystal display elements usually includes the following steps on a semiconductor substrate or glass substrate: a metal wiring formation step of setting a metal or metal oxide layer; a step of setting a photoresist layer; an exposure step of transferring a mask pattern on the photoresist; an etching step of etching the mold according to the pattern; and a stripping step of removing the photoresist. Photoresist stripping is a chemical reaction between a stripping solution and the photoresist that causes the photoresist to swell, soften, and dissolve.

[0003] However, in recent years, the ultra-fine trend of patterns caused by high-precision and high-integration in the component manufacturing process of semiconductor elements and liquid crystal elements has promoted the change of photoresist due to etching process, so it is necessary to improve its stripping ability. In addition, the change of metal wiring types used requires minimizing the corrosion effect on wiring.

[0004] General stripping solutions include inorganic acids, organic acids, inorganic bases or organic solvents. However, when inorganic acids or inorganic bases are used as the active ingredients of strippers, the lower metal film may be corroded or there may be disadvantages that are harmful to the human body, which may cause operational difficulties. Therefore, organic solvents are usually used. At present, the photoresist stripping solutions used in the manufacture of semiconductor elements and liquid crystal elements are mainly stripping solutions containing organic polar solvents, amines and water. However, these existing effective stripping solutions have the following problems: 1. Environmental safety, such as waste liquid treatment; 2. Weak stripping performance, which has a great impact on wiring corrosion; 3. The number of residual metal ions after cleaning exceeds the standard requirements, which is easy to cause surface metal ion contamination; 4. The production process is complicated. During the stripping process, after stripping off the photoresist, it is necessary to rinse with organic solvents and water respectively.

[0005] In the process of stripping and removal, the main problems that need to be solved are: oxidation corrosion of the substrate and residual glue. It is necessary to strip cleanly without residue and without damaging the copper substrate. The conventional practice in the prior art is to add azole protective agents, such as methylbenzalone, to protect the copper substrate. However, the introduced azole protective agents will produce additive residues, which will not be removed cleanly and will cause adverse effects such as increased surface current during subsequent use.

[0006] Therefore, based on material modification and preparation process improvement processing technology, this method proposes a preparation method and application of a hydrophilic stripping solution. The stripping solution has good stripping effect and high permeability. There is basically no residue on the surface of the substrate after cleaning. The production process basically does not involve toxic and harmful substances. The product has no corrosion hazard to the substrate and is suitable for industrial promotion. Summary of the invention

[0007] The present invention aims to provide a preparation method and application of a hydrophilic stripping solution, which has a good enhancement effect on the penetration and stripping effect of the stripping solution and the protection of the substrate through the improvement of relevant processes and raw materials.

[0008] The key points of this method are: 1. No excess waste should be generated during the modification of related raw materials, especially materials that cause pollution or damage to the cleaned substrate. Therefore, related reactions and ingredients need to be strictly calculated and the final product tested. 2. The ultimate goal of this method is to improve the cleaning effect of the hydrophilic stripping solution and reduce the corrosive effect on the cleaned substrate. Therefore, it is necessary to ensure the completeness of each reaction to avoid the participating materials or incomplete reactions affecting the performance of the product.

[0009] The specific implementation scheme of the preparation method of a hydrophilic stripping solution according to the present invention is as follows:

[0010] S1. The main reagent and auxiliary reagent of the hydrophilic stripping liquid raw material are configured in a mass ratio, wherein the main reagent includes a water-soluble organic solvent, a surfactant, a corrosion inhibitor, a dispersant, an organic amine, a penetrant, a protective agent, and deionized water;

[0011] Auxiliary reagents include aminosulfonic acid, butyl acrylate, ammonium persulfate, sodium bisulfite, and trimethylsilyl chloride;

[0012] According to the mass ratio, the main reagent is prepared as follows: 40-70 parts of a water-soluble organic solvent, 10-15 parts of a surfactant, 0.8-2.4 parts of a corrosion inhibitor, 0.1-0.5 parts of a dispersant, 4-16 parts of an organic amine, 5-10 parts of a penetrant, 1-3 parts of a protective agent, and 30-60 parts of deionized water;

[0013] The auxiliary reagents are prepared according to mass proportion: 10-15 parts of aminosulfonic acid, 0.2-1.25 parts of butyl acrylate, 0.01-0.015 parts of ammonium persulfate, 0.01-0.015 parts of sodium bisulfite, and 5-10 parts of trimethylchlorosilane;

[0014] Further, the water-soluble organic solvent is one or two of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monomethyl ether;

[0015] Further, the surfactant is alkylphenol polyoxyethylene ether;

[0016] Further, the corrosion inhibitor is a mixture of hydroxyethylidene diphosphonic acid, sodium tungstate, and zinc sulfate, with a mass ratio of 1:0.8-1.2:0.1-0.3;

[0017] Further wherein the dispersant is acrylic acid;

[0018] Further wherein the organic amine is ethanolamine;

[0019] Further, the penetrant is decyl polyoxyethylene ether;

[0020] Further, the protective agent is zinc borate;

[0021] S2. Modifying the raw materials of alkylphenol polyoxyethylene ether to obtain a modified surfactant comprises the following steps:

[0022] Take alkylphenol polyoxyethylene ether and stir it at 110-150° C. for 3-10 minutes, then add aminosulfonic acid in 3-5 batches and continue stirring for 60-120 minutes to obtain a modified surfactant;

[0023] S3. Modifying the acrylic acid raw material to obtain a modified dispersant, comprising the following steps:

[0024] Mix butyl acrylate and acrylic acid, then add ammonium persulfate and sodium bisulfite respectively, stir and react at 50-80°C for 20-40 minutes to obtain a modified dispersant;

[0025] S4. Modifying the raw materials of decyl polyoxyethylene ether to obtain a modified penetrant, comprising the following steps:

[0026] Take decyl polyoxyethylene ether and stir it at 40-60°C for 20-40 minutes, then add trimethylchlorosilane dropwise and continue stirring for 1-2 hours, and finally add sodium hydroxide solution dropwise until the pH value is 6.5-7.5 to obtain a modified penetrant;

[0027] S5. A hydrophilic stripping solution is prepared by mixing the reagents in S1-S4 by stirring and degassing;

[0028] Stirring: Mix the water-soluble organic solvent, corrosion inhibitor, organic amine, protective agent, deionized water in S1 with the modified surfactant, dispersant, and penetrant in S2-S4 and stir for 30-60 minutes;

[0029] Degassing: The stirred mixed solution is subjected to vacuum degassing to obtain the target hydrophilic stripping solution, with a vacuum degree of 0.1-0.01 MPa.

[0030] Beneficial effects:

[0031] (1) The method designed by the present invention adopts two ingredients, the main reagent and the auxiliary reagent, to modify some materials, thereby improving the wetting, penetration, cleaning and protection effects of the final product and reducing the production cost;

[0032] (2) The aqueous stripping liquid finally obtained in the method designed by the present invention has basically no corrosion to the cleaned substrate, and there is no residue or particulate matter on the surface after cleaning, and the cleanliness is good. The final product is non-toxic and non-irritating, and is easy to be discharged into waste liquid treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The present invention is a preparation flow chart of a preparation method and application of a hydrophilic stripping solution. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0035] The present invention provides a method for preparing a hydrophilic stripping solution, which mainly comprises the following steps:

[0036] S1. The main reagent and auxiliary reagent of the hydrophilic stripping liquid raw material are configured in a mass ratio;

[0037] S2. Modifying the raw materials of alkylphenol polyoxyethylene ether to obtain a modified surfactant;

[0038] S3. Modifying the acrylic acid raw material to obtain a modified dispersant;

[0039] S4. Modifying the raw materials of decyl polyoxyethylene ether to obtain a modified penetrant;

[0040] S5. A hydrophilic stripping solution is prepared by mixing the reagents in S1-S4 by stirring and degassing;

[0041] As an embodiment, the following contents of the embodiments of the present invention provide several specific examples of the preparation method and application of the aforementioned hydrophilic stripping solution, such as Example 1, Example 2, Example 3 and Examples 1-7 for comparison and explanation.

[0042] Embodiment 1:

[0043] S1. The main reagent and auxiliary reagent of the hydrophilic stripping liquid raw material are configured by mass, wherein the main reagent is a water-soluble organic solvent, a surfactant, a corrosion inhibitor, a dispersant, an organic amine mixture, a penetrant, a protective agent and deionized water;

[0044] The auxiliary reagents are aminosulfonic acid, butyl acrylate, ammonium persulfate, sodium bisulfite and trimethylsilyl chloride;

[0045] The main reagents are composed of: 40 parts of water-soluble organic solvent, 10 parts of surfactant, 0.8 parts of corrosion inhibitor, 0.1 parts of dispersant, 4 parts of organic amine, 5 parts of penetrant, 1 part of protective agent, and 30 parts of deionized water;

[0046] The auxiliary reagents are composed of: 10 parts of aminosulfonic acid, 0.2 parts of butyl acrylate, 0.01 parts of ammonium persulfate, 0.01 parts of sodium bisulfite, and 5 parts of trimethylchlorosilane;

[0047] The water-soluble organic solvent is ethylene glycol monomethyl ether;

[0048] The surfactant is alkylphenol polyoxyethylene ether;

[0049] The corrosion inhibitor is hydroxyethylidene diphosphonic acid, sodium tungstate, and zinc sulfate in a mass ratio of 1:0.8:0.1;

[0050] The dispersant is acrylic acid;

[0051] The organic amine is ethanolamine;

[0052] The penetrant is decyl polyoxyethylene ether;

[0053] The protective agent is zinc borate;

[0054] S2. Modifying the raw materials of alkylphenol polyoxyethylene ether to obtain a modified surfactant comprises the following steps:

[0055] 12 parts of alkylphenol polyoxyethylene ether were stirred at 110° C. for 3 minutes, and then 6 parts of aminosulfonic acid were added in 3 batches and stirred for 60 minutes to obtain a modified surfactant;

[0056] S3. Modifying the acrylic acid raw material to obtain a modified dispersant, comprising the following steps:

[0057] 10 parts of butyl acrylate and 10 parts of acrylic acid were mixed, and then 2 parts of ammonium persulfate and 0.5 parts of sodium bisulfite were added respectively, and stirred at 50°C for 20 minutes to obtain a modified dispersant;

[0058] S4. Modifying the raw materials of decyl polyoxyethylene ether to obtain a modified penetrant, comprising the following steps:

[0059] Take 8 parts of decyl polyoxyethylene ether and stir at 40°C for 20 minutes, then add 1 part of trimethylsilyl chloride and continue stirring for 1 hour, and finally add sodium hydroxide solution until the pH value is 7 to obtain a modified penetrant;

[0060] S5. A hydrophilic stripping solution is prepared by mixing the reagents in S1-S4 by stirring and degassing;

[0061] Stirring: Mix the water-soluble organic solvent, corrosion inhibitor, organic amine, protective agent, deionized water in S1 with the modified surfactant, dispersant, and penetrant in S2-S4 and stir for 30 minutes;

[0062] Degassing: The stirred mixed solution is subjected to vacuum degassing to obtain the target hydrophilic stripping solution, and the vacuum degree is 0.1 MPa.

[0063] Embodiment 2:

[0064] S1. The main reagent and auxiliary reagent of the hydrophilic stripping liquid raw material are configured in a mass ratio, wherein the main reagent includes a water-soluble organic solvent, a surfactant, a corrosion inhibitor, a dispersant, an organic amine mixture, a penetrant, a protective agent, and deionized water;

[0065] Auxiliary reagents include aminosulfonic acid, butyl acrylate, ammonium persulfate, sodium bisulfite, and trimethylsilyl chloride;

[0066] According to the mass ratio, the main reagent is prepared as follows: 70 parts of water-soluble organic solvent, 15 parts of surfactant, 2.4 parts of corrosion inhibitor, 0.5 parts of dispersant, 16 parts of organic amine, 10 parts of penetrant, 3 parts of protective agent, and 60 parts of deionized water;

[0067] The auxiliary reagents are prepared according to the mass ratio: 15 parts of aminosulfonic acid, 1.25 parts of butyl acrylate, 0.015 parts of ammonium persulfate, 0.015 parts of sodium bisulfite, and 10 parts of trimethylchlorosilane;

[0068] Further, the water-soluble organic solvent is ethylene glycol monomethyl ether;

[0069] Further, the surfactant is alkylphenol polyoxyethylene ether;

[0070] Further, the corrosion inhibitor is a mixture of hydroxyethylidene diphosphonic acid, sodium tungstate, and zinc sulfate, with a mass ratio of 1:1.2:0.3;

[0071] Further wherein the dispersant is acrylic acid;

[0072] Further wherein the organic amine is ethanolamine;

[0073] Further, the penetrant is decyl polyoxyethylene ether;

[0074] Further, the protective agent is zinc borate;

[0075] S2. Modifying the raw materials of alkylphenol polyoxyethylene ether to obtain a modified surfactant comprises the following steps:

[0076] 14 parts of alkylphenol polyoxyethylene ether were stirred at 150° C. for 10 minutes, and then 8 parts of aminosulfonic acid were added in 5 batches and stirred for 120 minutes to obtain a modified surfactant;

[0077] S3. Modifying the acrylic acid raw material to obtain a modified dispersant, comprising the following steps:

[0078] 12 parts of butyl acrylate and 12 parts of acrylic acid were mixed, and then 2.4 parts of ammonium persulfate and 0.8 parts of sodium bisulfite were added respectively, and stirred at 80° C. for 40 minutes to obtain a modified dispersant;

[0079] S4. Modifying the raw materials of decyl polyoxyethylene ether to obtain a modified penetrant, comprising the following steps:

[0080] Take 10 parts of decyl polyoxyethylene ether and stir at 60°C for 40 minutes, then add 1.5 parts of trimethylsilyl chloride and continue stirring for 2 hours, and finally add sodium hydroxide solution until the pH value is 7 to obtain a modified penetrant;

[0081] S5. A hydrophilic stripping solution is prepared by mixing the reagents in S1-S4 by stirring and degassing;

[0082] Stirring: Mix the water-soluble organic solvent, corrosion inhibitor, organic amine, protective agent, deionized water in S1 with the modified surfactant, dispersant, and penetrant in S2-S4 and stir for 60 minutes;

[0083] Degassing: The stirred mixed solution is subjected to vacuum degassing to obtain the target hydrophilic stripping solution, and the vacuum degree is 0.01 MPa.

[0084] Embodiment 3:

[0085] S1. The main reagent and auxiliary reagent of the hydrophilic stripping liquid raw material are configured in a mass ratio, wherein the main reagent includes a water-soluble organic solvent, a surfactant, a corrosion inhibitor, a dispersant, an organic amine mixture, a penetrant, a protective agent, and deionized water;

[0086] Auxiliary reagents include aminosulfonic acid, butyl acrylate, ammonium persulfate, sodium bisulfite, and trimethylsilyl chloride;

[0087] According to the mass ratio, the main reagent is prepared as follows: 60 parts of water-soluble organic solvent, 12 parts of surfactant, 1.6 parts of corrosion inhibitor, 0.3 parts of dispersant, 10 parts of organic amine, 8 parts of penetrant, 2 parts of protective agent, and 40 parts of deionized water;

[0088] The auxiliary reagents are prepared according to the mass ratio: 12 parts of aminosulfonic acid, 0.8 parts of butyl acrylate, 0.013 parts of ammonium persulfate, 0.013 parts of sodium bisulfite, and 8 parts of trimethylchlorosilane;

[0089] Further, the water-soluble organic solvent is ethylene glycol monomethyl ether;

[0090] Further, the surfactant is alkylphenol polyoxyethylene ether;

[0091] Further, the corrosion inhibitor is a mixture of hydroxyethylidene diphosphonic acid, sodium tungstate, and zinc sulfate, with a mass ratio of 1:1:0.2;

[0092] Further wherein the dispersant is acrylic acid;

[0093] Further wherein the organic amine is ethanolamine;

[0094] Further, the penetrant is decyl polyoxyethylene ether;

[0095] Further, the protective agent is zinc borate;

[0096] S2. Modifying the raw materials of alkylphenol polyoxyethylene ether to obtain a modified surfactant comprises the following steps:

[0097] Alkylphenol polyoxyethylene ether was stirred at 130° C. for 6 min, and then aminosulfonic acid was added in 4 batches and stirred for 80 min to obtain a modified surfactant;

[0098] S3. Modifying the acrylic acid raw material to obtain a modified dispersant, comprising the following steps:

[0099] Mix butyl acrylate and acrylic acid, then add ammonium persulfate and sodium bisulfite respectively, stir and react at 60°C for 30 minutes to obtain a modified dispersant;

[0100] S4. Modifying the raw materials of decyl polyoxyethylene ether to obtain a modified penetrant, comprising the following steps:

[0101] Take decyl polyoxyethylene ether and stir it at 50°C for 30 minutes, then add trimethylchlorosilane dropwise and continue stirring for 1.5 hours, and finally add sodium hydroxide solution dropwise until the pH value reaches 7 to obtain a modified penetrant;

[0102] S5. A hydrophilic stripping solution is prepared by mixing the reagents in S1-S4 by stirring and degassing;

[0103] Stirring: Mix the water-soluble organic solvent, corrosion inhibitor, organic amine, protective agent, deionized water in S1 with the modified surfactant, dispersant, and penetrant in S2-S4 and stir for 40 minutes;

[0104] Degassing: The stirred mixed solution is subjected to vacuum degassing to obtain the target hydrophilic stripping solution, and the vacuum degree is 0.05 MPa.

[0105] Comparative Example 1:

[0106] S1. Prepare hydrophilic stripping liquid raw materials according to mass ratio, including water-soluble organic solvent, surfactant, corrosion inhibitor, dispersant, organic amine mixture, penetrant, protective agent, and deionized water;

[0107] According to the mass ratio, the reagents are prepared as follows: 60 parts of water-soluble organic solvent, 12 parts of surfactant, 1.6 parts of corrosion inhibitor, 0.3 parts of dispersant, 10 parts of organic amine, 8 parts of penetrant, 2 parts of protective agent, and 40 parts of deionized water;

[0108] Further, the water-soluble organic solvent is ethylene glycol monomethyl ether;

[0109] Further, the surfactant is alkylphenol polyoxyethylene ether;

[0110] Further, the corrosion inhibitor is a mixture of hydroxyethylidene diphosphonic acid, sodium tungstate, and zinc sulfate, with a mass ratio of 1:1:0.2;

[0111] Further wherein the dispersant is acrylic acid;

[0112] Further wherein the organic amine is ethanolamine;

[0113] Further, the penetrant is decyl polyoxyethylene ether;

[0114] Further, the protective agent is zinc borate;

[0115] S2. The raw materials in S1 are mixed by stirring and degassing to obtain a hydrophilic stripping solution;

[0116] Stirring: Mix the water-soluble organic solvent, corrosion inhibitor, organic amine, protective agent, deionized water, surfactant, dispersant and penetrant in S1 and stir for 40 minutes;

[0117] Degassing: The stirred mixed solution is subjected to vacuum degassing to obtain the target hydrophilic stripping solution, and the vacuum degree is 0.05 MPa.

[0118] Comparative Example 2:

[0119] S1. The main reagent and auxiliary reagent of the hydrophilic stripping liquid raw material are configured in a mass ratio, wherein the main reagent includes a water-soluble organic solvent, a surfactant, a corrosion inhibitor, a dispersant, an organic amine mixture, a penetrant, a protective agent, and deionized water;

[0120] Auxiliary reagents include butyl acrylate, ammonium persulfate, sodium bisulfite, and trimethylsilyl chloride;

[0121] According to the mass ratio, the main reagent is prepared as follows: 60 parts of water-soluble organic solvent, 12 parts of surfactant, 1.6 parts of corrosion inhibitor, 0.3 parts of dispersant, 10 parts of organic amine, 8 parts of penetrant, 2 parts of protective agent, and 40 parts of deionized water;

[0122] The auxiliary reagents butyl acrylate 0.8 parts, ammonium persulfate 0.013 parts, sodium bisulfite 0.013 parts, and trimethylchlorosilane 8 parts were prepared according to the mass ratio;

[0123] Further, the water-soluble organic solvent is ethylene glycol monomethyl ether;

[0124] Further, the surfactant is alkylphenol polyoxyethylene ether;

[0125] Further, the corrosion inhibitor is a mixture of hydroxyethylidene diphosphonic acid, sodium tungstate, and zinc sulfate, with a mass ratio of 1:1:0.2;

[0126] Further wherein the dispersant is acrylic acid;

[0127] Further wherein the organic amine is ethanolamine;

[0128] Further, the penetrant is decyl polyoxyethylene ether;

[0129] Further, the protective agent is zinc borate;

[0130] S2. Modify the acrylic acid to obtain a modified dispersant (same as Example 1).

[0131] S3. Modify the raw materials of decyl polyoxyethylene ether to obtain a modified penetrant (same as Example 1).

[0132] S4. A hydrophilic stripping solution is prepared by mixing the reagents in S1-S3 by stirring and degassing;

[0133] Stirring: Mix the water-soluble organic solvent, corrosion inhibitor, organic amine, protective agent, surfactant, deionized water in S1 with the modified dispersant and penetrant in S2-S3 and stir for 40 minutes;

[0134] Degassing: The stirred mixed solution is subjected to vacuum degassing to obtain the target hydrophilic stripping solution, and the vacuum degree is 0.05 MPa.

[0135] Comparative Example 3:

[0136] S1. The main reagent and auxiliary reagent of the hydrophilic stripping liquid raw material are configured in a mass ratio, wherein the main reagent includes a water-soluble organic solvent, a surfactant, a corrosion inhibitor, a dispersant, an organic amine mixture, a penetrant, a protective agent, and deionized water;

[0137] Auxiliary reagents include aminosulfonic acid and trimethylsilyl chloride;

[0138] According to the mass ratio, the main reagent is prepared as follows: 60 parts of water-soluble organic solvent, 12 parts of surfactant, 1.6 parts of corrosion inhibitor, 0.3 parts of dispersant, 10 parts of organic amine, 8 parts of penetrant, 2 parts of protective agent, and 40 parts of deionized water;

[0139] According to the mass ratio, 12 parts of the auxiliary reagent aminosulfonic acid and 8 parts of trimethylchlorosilane were prepared;

[0140] Further, the water-soluble organic solvent is ethylene glycol monomethyl ether;

[0141] Further, the surfactant is alkylphenol polyoxyethylene ether;

[0142] Further, the corrosion inhibitor is a mixture of hydroxyethylidene diphosphonic acid, sodium tungstate, and zinc sulfate, with a mass ratio of 1:1:0.2;

[0143] Further wherein the dispersant is acrylic acid;

[0144] Further wherein the organic amine is ethanolamine;

[0145] Further, the penetrant is decyl polyoxyethylene ether;

[0146] Further, the protective agent is zinc borate;

[0147] S2. The alkylphenol polyoxyethylene ether is subjected to raw material modification to obtain a modified surfactant (same as in Example 2);

[0148] S3. The raw material of decyl polyoxyethylene ether is modified to obtain a modified penetrant (same as in Example 2);

[0149] S4. A hydrophilic stripping solution is prepared by mixing the reagents in S1-S3 by stirring and degassing;

[0150] Stirring: Mix the water-soluble organic solvent, corrosion inhibitor, organic amine, protective agent, dispersant, deionized water in S1 with the modified surfactant and penetrant in S2-S3 and stir for 40 minutes;

[0151] Degassing: The stirred mixed solution is subjected to vacuum degassing to obtain the target hydrophilic stripping solution, and the vacuum degree is 0.05 MPa.

[0152] Comparative Example 4:

[0153] S1. The main reagent and auxiliary reagent of the hydrophilic stripping liquid raw material are configured in a mass ratio, wherein the main reagent includes a water-soluble organic solvent, a surfactant, a corrosion inhibitor, a dispersant, an organic amine mixture, a penetrant, a protective agent, and deionized water;

[0154] Auxiliary reagents include aminosulfonic acid, butyl acrylate, ammonium persulfate, and sodium bisulfite;

[0155] According to the mass ratio, the main reagent is prepared as follows: 60 parts of water-soluble organic solvent, 12 parts of surfactant, 1.6 parts of corrosion inhibitor, 0.3 parts of dispersant, 10 parts of organic amine, 8 parts of penetrant, 2 parts of protective agent, and 40 parts of deionized water;

[0156] The auxiliary reagents are prepared according to the mass ratio: 12 parts of aminosulfonic acid, 0.8 parts of butyl acrylate, 0.013 parts of ammonium persulfate, and 0.013 parts of sodium bisulfite;

[0157] Further, the water-soluble organic solvent is ethylene glycol monomethyl ether;

[0158] Further, the surfactant is alkylphenol polyoxyethylene ether;

[0159] Further, the corrosion inhibitor is a mixture of hydroxyethylidene diphosphonic acid, sodium tungstate, and zinc sulfate, with a mass ratio of 1:1:0.2;

[0160] Further wherein the dispersant is acrylic acid;

[0161] Further wherein the organic amine is ethanolamine;

[0162] Further, the penetrant is decyl polyoxyethylene ether;

[0163] Further, the protective agent is zinc borate;

[0164] S2. The alkylphenol polyoxyethylene ether is subjected to raw material modification to obtain a modified surfactant (same as in Example 1);

[0165] S3. The acrylic acid raw material is modified to obtain a modified dispersant (same as in Example 1);

[0166] S5. A hydrophilic stripping solution (same as in Example 1) is prepared by mixing the reagents in S1-S3 by stirring and degassing;

[0167] Degassing: The stirred mixed solution is subjected to vacuum degassing to obtain the target hydrophilic stripping solution, and the vacuum degree is 0.05 MPa.

[0168] Comparative Example 5:

[0169] S1. The main reagent and auxiliary reagent of the hydrophilic stripping liquid raw material are configured in a mass ratio, wherein the main reagent includes a water-soluble organic solvent, a surfactant, a dispersant, an organic amine mixture, a penetrant, a protective agent, and deionized water;

[0170] Auxiliary reagents include aminosulfonic acid, butyl acrylate, ammonium persulfate, sodium bisulfite, and trimethylsilyl chloride;

[0171] According to the mass ratio, the main reagent is prepared as follows: 60 parts of water-soluble organic solvent, 12 parts of surfactant, 0.3 parts of dispersant, 10 parts of organic amine, 8 parts of penetrant, 2 parts of protective agent, and 40 parts of deionized water;

[0172] The auxiliary reagents are prepared according to the mass ratio: 12 parts of aminosulfonic acid, 0.8 parts of butyl acrylate, 0.013 parts of ammonium persulfate, 0.013 parts of sodium bisulfite, and 8 parts of trimethylchlorosilane;

[0173] Further, the water-soluble organic solvent is ethylene glycol monomethyl ether;

[0174] Further, the surfactant is alkylphenol polyoxyethylene ether;

[0175] Further wherein the dispersant is acrylic acid;

[0176] Further wherein the organic amine is ethanolamine;

[0177] Further, the penetrant is decyl polyoxyethylene ether;

[0178] Further, the protective agent is zinc borate;

[0179] S2. The alkylphenol polyoxyethylene ether is subjected to raw material modification to obtain a modified surfactant (same as in Example 1);

[0180] S3. The acrylic acid raw material is modified to obtain a modified dispersant (same as in Example 1);

[0181] S4. The raw material of decyl polyoxyethylene ether is modified to obtain a modified penetrant (same as in Example 1);

[0182] S5. A hydrophilic stripping solution is prepared by mixing the reagents in S1-S4 by stirring and degassing;

[0183] Stirring: Mix the water-soluble organic solvent, organic amine, protective agent, deionized water in S1 with the modified surfactant, dispersant, and penetrant in S2-S4 and stir for 40 minutes;

[0184] Degassing: The stirred mixed solution is subjected to vacuum degassing to obtain the target hydrophilic stripping solution, and the vacuum degree is 0.05 MPa.

[0185] Comparative Example 6:

[0186] S1. The main reagent and auxiliary reagent of the hydrophilic stripping liquid raw material are configured in a mass ratio, wherein the main reagent includes a water-soluble organic solvent, a surfactant, a corrosion inhibitor, a dispersant, an organic amine mixture, a penetrant, a protective agent, and deionized water;

[0187] Auxiliary reagents include aminosulfonic acid, butyl acrylate, ammonium persulfate, sodium bisulfite, and trimethylsilyl chloride;

[0188] According to the mass ratio, the main reagent is prepared as follows: 60 parts of water-soluble organic solvent, 12 parts of surfactant, 1.6 parts of corrosion inhibitor, 0.3 parts of dispersant, 10 parts of organic amine, 8 parts of penetrant, 2 parts of protective agent, and 40 parts of deionized water;

[0189] The auxiliary reagents are prepared according to the mass ratio: 12 parts of aminosulfonic acid, 0.8 parts of butyl acrylate, 0.013 parts of ammonium persulfate, 0.013 parts of sodium bisulfite, and 8 parts of trimethylchlorosilane;

[0190] Further, the water-soluble organic solvent is ethylene glycol monomethyl ether;

[0191] Further, the surfactant is alkylphenol polyoxyethylene ether;

[0192] Further, the corrosion inhibitor is hydroxyethylidene diphosphonic acid;

[0193] Further wherein the dispersant is acrylic acid;

[0194] Further wherein the organic amine is ethanolamine;

[0195] Further, the penetrant is decyl polyoxyethylene ether;

[0196] Further, the protective agent is zinc borate;

[0197] S2. The alkylphenol polyoxyethylene ether is subjected to raw material modification to obtain a modified surfactant (same as in Example 2);

[0198] S3. The acrylic acid raw material is modified to obtain a modified dispersant (same as in Example 2);

[0199] S4. The raw material of decyl polyoxyethylene ether is modified to obtain a modified penetrant (same as in Example 2);

[0200] S5. A hydrophilic stripping solution is prepared by mixing the reagents in S1-S4 by stirring and degassing;

[0201] Stirring: Mix the water-soluble organic solvent, corrosion inhibitor, organic amine, protective agent, deionized water in S1 with the modified surfactant, dispersant, and penetrant in S2-S4 and stir for 40 minutes;

[0202] Degassing: The stirred mixed solution is subjected to vacuum degassing to obtain the target hydrophilic stripping solution, and the vacuum degree is 0.05 MPa.

[0203] Comparative Example 7:

[0204] S1. The main reagent and auxiliary reagent of the hydrophilic stripping liquid raw material are configured in a mass ratio, wherein the main reagent includes a water-soluble organic solvent, a surfactant, a corrosion inhibitor, a dispersant, an organic amine mixture, a penetrant, a protective agent, and deionized water;

[0205] Auxiliary reagents include aminosulfonic acid, butyl acrylate, ammonium persulfate, sodium bisulfite, and trimethylsilyl chloride;

[0206] According to the mass ratio, the main reagent is prepared as follows: 60 parts of water-soluble organic solvent, 12 parts of surfactant, 1.6 parts of corrosion inhibitor, 0.3 parts of dispersant, 10 parts of organic amine, 8 parts of penetrant, 2 parts of protective agent, and 40 parts of deionized water;

[0207] The auxiliary reagents are prepared according to the mass ratio: 12 parts of aminosulfonic acid, 0.8 parts of butyl acrylate, 0.013 parts of ammonium persulfate, 0.013 parts of sodium bisulfite, and 8 parts of trimethylchlorosilane;

[0208] Further, the water-soluble organic solvent is ethylene glycol monomethyl ether;

[0209] Further, the surfactant is alkylphenol polyoxyethylene ether;

[0210] Further, the corrosion inhibitor is a mixture of hydroxyethylidene diphosphonic acid, sodium tungstate, and zinc sulfate, with a mass ratio of 1:1:0.2;

[0211] Further wherein the dispersant is acrylic acid;

[0212] Further wherein the organic amine is ethanolamine;

[0213] Further, the penetrant is decyl polyoxyethylene ether;

[0214] Further, the protective agent is zinc borate;

[0215] S2. The alkylphenol polyoxyethylene ether is subjected to raw material modification to obtain a modified surfactant (same as in Example 1);

[0216] S3. The acrylic acid raw material is modified to obtain a modified dispersant (same as in Example 1);

[0217] S4. The raw material of decyl polyoxyethylene ether is modified to obtain a modified penetrant (same as in Example 1);

[0218] S5. A hydrophilic stripping solution is prepared by mixing the reagents in S1-S4 with stirring;

[0219] Stirring: The water-soluble organic solvent, corrosion inhibitor, organic amine, protective agent, and deionized water in S1 are mixed with the modified surfactant, dispersant, and penetrant in S2-S4 and stirred for 40 minutes to obtain the target hydrophilic stripping solution.

[0220] Visual observation:

[0221] Lighting conditions: 20W incandescent lamp or 40W fluorescent lamp, the ambient light brightness requirement is 800LUX;

[0222] The inspector's vision must be above 1.0 (including corrected vision);

[0223] Observe at 100 times:

[0224] Use an optical microscope to take photos of the cleaned samples at 100 times magnification;

[0225] Corrosion pitting assessment:

[0226] The national standard for corrosion severity is mainly based on the comprehensive assessment of the degree of damage to building materials by corrosive media, and is divided into four levels: strong corrosion, medium corrosion, weak corrosion, and no corrosion. This classification takes into account factors such as the changes in the appearance, weight change, strength loss, and corrosion rate of building materials caused by corrosive media. For details, please refer to GB / T18590-2001 Corrosion pitting assessment method for metals and alloys. The test results are shown in Table 1.

[0227] Table 1: Effect test

[0228]

[0229] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the purpose and scope of the technical solution, which should be included in the scope of the claims of the present invention.

Claims

1. A method for preparing a hydrophilic stripping solution, characterized in that: The steps include: S1. The main reagent and auxiliary reagent of the hydrophilic stripping liquid raw material are configured in a mass ratio; S2. Modifying the raw materials of alkylphenol polyoxyethylene ether to obtain a modified surfactant; S3. Modifying the acrylic acid raw material to obtain a modified dispersant; S4. Modifying the raw materials of decyl polyoxyethylene ether to obtain a modified penetrant; S5. A hydrophilic stripping solution is prepared by mixing the reagents in S1-S4 by stirring and degassing; In step S1, the main reagents include: a water-soluble organic solvent, a surfactant, a corrosion inhibitor, a dispersant, an organic amine, a penetrant, a protective agent, and deionized water; In step S1, the auxiliary reagents include: aminosulfonic acid, butyl acrylate, ammonium persulfate, sodium bisulfite, and trimethylchlorosilane; In step S1, the main reagent raw material composition is: The water-soluble organic solvent is one or two of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monomethyl ether; The surfactant is alkylphenol polyoxyethylene ether; The corrosion inhibitor is a mixture of hydroxyethylidene diphosphonic acid, sodium tungstate and zinc sulfate, with a mass ratio of 1: (0.8-1.2): (0.1-0.3); The dispersant is acrylic acid; The organic amine is ethanolamine; The penetrant is decyl polyoxyethylene ether; The protective agent is zinc borate.

2. The preparation method according to claim 1, characterized in that: In step S1, the main reagent raw materials are measured by mass as follows: 40-70 parts of water-soluble organic solvent, 10-15 parts of surfactant, 0.8-2.4 parts of corrosion inhibitor, 0.1-0.5 parts of dispersant, 4-16 parts of organic amine, 5-10 parts of penetrant, 1-3 parts of protective agent, and 30-60 parts of deionized water.

3. The preparation method according to claim 1, characterized in that: In step S1, the auxiliary reagent raw materials are measured by mass as follows: 10-15 parts of aminosulfonic acid, 0.2-1.25 parts of butyl acrylate, 0.01-0.015 parts of ammonium persulfate, 0.01-0.015 parts of sodium bisulfite, and 5-10 parts of trimethylchlorosilane.

4. The preparation method according to claim 1, characterized in that: In step S2, the process of modifying the alkylphenol polyoxyethylene ether to obtain a modified surfactant comprises: stirring the alkylphenol polyoxyethylene ether at 110-150° C. for 3-10 minutes, then adding aminosulfonic acid in 3-5 batches and continuing to stir for 60-120 minutes to obtain the modified surfactant.

5. The preparation method according to claim 1, characterized in that: In step S3, the process of modifying acrylic acid to obtain a modified dispersant includes: mixing butyl acrylate and acrylic acid, and then adding ammonium persulfate and sodium bisulfite respectively, stirring and reacting at 50-80° C. for 20-40 minutes to obtain a modified dispersant.

6. The preparation method according to claim 1, characterized in that: In step S4, the process of modifying the raw material of decyl polyoxyethylene ether to obtain a modified penetrant includes: taking decyl polyoxyethylene ether and stirring it at 40-60° C. for 20-40 minutes, then adding trimethylchlorosilane and continuing to stir for 1-2 hours, and finally adding sodium hydroxide solution to a pH value of 6.5-7.5 to obtain a modified penetrant.

7. A use of the hydrophilic stripping solution according to any one of claims 1 to 6, characterized in that: The hydrophilic stripping liquid material can be used for stripping photoresist during production of semiconductor elements or liquid crystal display elements.

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