Stripping liquid composition as well as preparation method and application thereof

Abstract

The invention provides a stripping liquid composition as well as a preparation method and application thereof, and particularly relates to the technical field of photoetching. The stripping liquid composition comprises organic alkali, a glycol ether solvent, a ketal solvent, nylon acid methyl ester, a protective agent, a beta-cyclodextrin derivative and pure water, the organic base comprises sterically hindered alcohol amine and a bicyclic guanidine compound. According to the invention, the combination of steric hindrance alcohol amine and bicyclic guanidine compound acts on the photoresist, so that the macromolecular structure of the photoresist can be effectively damaged, the corrosion is smaller than that of other strong bases, and introduction of a large number of removable alkali metal ions is avoided. The glycol ether solvent, the ketal solvent and the nylon acid methyl ester are matched to provide better dissolving and stripping effects; the protective agent realizes efficient protection of the wiring film; the beta-cyclodextrin derivative not only can wet the photoresist and increase the capacity of decomposed particles of the photoresist, but also can prolong the storage stability of the stripping liquid. All the components cooperate with one another, so that the stripping effect, the application range and the storage stability are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of photolithography, and in particular to a stripping liquid composition, a preparation method thereof and an application thereof. Background Art

[0002] The photoresist stripping process is a critical step in the manufacturing of various display panels. After the etching process, this process requires thorough cleaning of the photoresist attached to the wiring film layer to ensure no residual photoresist and re-adsorption of photoresist particles. Furthermore, the stripping process must not cause corrosion or discoloration to the wiring film layer, as this would adversely affect subsequent device processing steps, leading to reduced device performance and even failure.

[0003] With the rapid development of the display panel industry, end-consumer usage scenarios and demands are becoming increasingly diverse. The TFT process structure, as well as the metal and metal oxide materials used as wiring in mainstream displays, such as thin-film transistor liquid crystal displays (TFT-LCDs) and organic light-emitting diode displays (OLEDs), are also showing a trend of diversification. Metallic wiring materials primarily include molybdenum, aluminum, copper, and silver films. To meet the performance requirements of large display screens, high resolution, high contrast, high refresh rates, and high reliability, the critical dimensions of processed wiring materials must be continuously reduced, and control over circuit fineness must be tightened. Furthermore, to reduce operating costs and waste stripping fluid disposal costs, stripping fluids must exhibit excellent process tolerance, process compatibility, and low toxicity. This places higher demands on the stripping fluid's stripping performance, corrosion inhibition, and environmental friendliness.

[0004] However, existing photoresist stripping liquid products still have the following shortcomings: 1. The stripping solution formula uses nitrogen-containing toxic solvents such as N-methylpyrrolidone, N-methylformamide, N,N-dimethylformamide, etc., which are harmful to the human body.

[0005] 2. The stripping process of different products is not compatible enough, which may easily lead to incomplete stripping or re-stickiness of photoresist particles. It is necessary to develop multiple stripping liquid products for matching.

[0006] 3. It can only meet the corrosion resistance requirements of a single type of aluminum or copper process, cannot achieve compatibility and adaptability with multiple processes, and gradually cannot meet the needs of technological development.

[0007] Therefore, it is particularly urgent to develop a composition that can be used for removing photoresist on various wiring film layers.

[0008] In view of this, the present invention is proposed. Summary of the Invention

[0009] The object of the present invention is to provide a stripping liquid composition and a preparation method and application thereof, aiming to solve at least one of the above-mentioned technical problems in the prior art.

[0010] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are adopted: The first aspect of the present invention provides a stripping solution composition comprising an organic base, a glycol ether solvent, a ketal solvent, methyl nylonate, a protective agent, a β-cyclodextrin derivative and pure water; the organic base comprises a hindered alcoholamine and a bicyclic guanidine compound.

[0011] Furthermore, the stripping solution composition includes 7-23 wt% of an organic base, 15-65 wt% of a glycol ether solvent, 15-55 wt% of a ketal solvent, 2-10 wt% of methyl nylonate, 0.5-4.5 wt% of a protective agent, 0.4-5 wt% of a β-cyclodextrin derivative, and the balance is pure water.

[0012] Furthermore, when the content of the organic base is 7-13 wt %, the usage ratio of the bicyclic guanidine compound to the hindered alcoholamine is 0.18-12.

[0013] Preferably, when the content of the organic base is 13-23 wt % (excluding 13 wt %), the usage ratio of the bicyclic guanidine compound to the hindered alcoholamine is 0.095-6.

[0014] Furthermore, the hindered alcoholamine is selected from at least one of 2-amino-2-methyl-1-propanol, N,N-diethylethanolamine, N,N-dimethylethanolamine, and 2-amino-2-ethyl-1,3-propanediol.

[0015] Preferably, the bicyclic guanidine compound is at least one selected from 1,5-diazabicyclo[4.3.0]non-5-ene and its derivatives, and 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0016] Preferably, the glycol ether solvent is at least one of diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monobutyl ether.

[0017] Preferably, the ketal solvent is at least one of acetone glycerol acetal, butanone glycerol acetal and cyclohexanone glycerol acetal.

[0018] Furthermore, the nylon acid methyl ester includes nylon acid dimethyl ester and / or mixed dibasic acid dimethyl ester.

[0019] Preferably, the protective agent comprises an imidazoline compound and / or a sugar amine compound.

[0020] Preferably, the imidazoline compound includes at least one of octyl hydroxyethyl imidazoline, 2-tridecyl-1-aminoethyl imidazoline, coconut oil hydroxyethyl imidazoline, lauryl hydroxyethyl imidazoline, and 2-undecyl-N-carboxymethyl-N-hydroxyethyl imidazoline.

[0021] Preferably, the sugar amine compound includes at least one of 1-amino-1-deoxy-β-D-galactose, 1-amino-2,5-anhydro-1-deoxy-D-mannitol, 1-deoxy-1-amino-β-glucose, 1-amino-β-D-galactose, and β-D-mannosylamine.

[0022] Preferably, the protective agent comprises an imidazoline compound and a sugar amine compound in a mass ratio of (0.4-6):1.

[0023] Preferably, the β-cyclodextrin derivative includes at least one of hydroxyethyl-β-cyclodextrin, hydroxypropyl-β-cyclodextrin, carboxymethyl-β-cyclodextrin, mono-(6-amino-6-deoxy)-β-cyclodextrin, and mono-(6-mercapto-6-deoxy)-β-cyclodextrin.

[0024] Preferably, the pure water comprises ultrapure water.

[0025] The second aspect of the present invention provides a method for preparing the stripping liquid composition, which comprises first uniformly mixing an organic base, a glycol ether solvent, a ketal solvent, methyl nylonate, a β-cyclodextrin derivative and pure water, and finally adding a protective agent, mixing uniformly and filtering to obtain the stripping liquid composition.

[0026] Furthermore, the filtration is divided into primary filtration and secondary filtration.

[0027] Preferably, the filter mesh used in the first-stage filtration has a pore size of 0.45 μm.

[0028] Preferably, the filter mesh used for the secondary filtration has a pore size of 0.1 μm.

[0029] The third aspect of the present invention provides the use of the stripping solution composition in removing photoresist on a metal film.

[0030] Furthermore, the metal film includes a molybdenum film, an aluminum film, a copper film or a silver film; Preferably, the molybdenum-based film includes a pure molybdenum film or a molybdenum-niobium film.

[0031] Preferably, the aluminum-based film includes aluminum / molybdenum film, aluminum / molybdenum-niobium film, aluminum-neodymium-molybdenum film, molybdenum / aluminum / molybdenum film, molybdenum-niobium / aluminum film, molybdenum / aluminum-neodymium film, aluminum / titanium film or titanium / aluminum / titanium film.

[0032] Preferably, the copper-based film includes copper film, copper / molybdenum film, copper / molybdenum niobium film, copper / molybdenum titanium film, copper / molybdenum titanium nickel film, molybdenum titanium nickel / copper / molybdenum titanium nickel film, molybdenum titanium nickel / copper / molybdenum titanium film or molybdenum niobium / copper / molybdenum titanium nickel film.

[0033] Preferably, the silver-based film includes a silver film, an indium tin oxide / silver film, or an indium tin oxide / silver / indium tin oxide film.

[0034] Compared with the prior art, the present invention has at least the following beneficial effects: The stripping solution composition provided by the present invention effectively destroys the photoresist's macromolecular structure through the combined action of a hindered alcoholamine and a bicyclic guanidine compound. The hindered alcoholamine exhibits less corrosiveness than other strong bases, such as unhindered alcoholamines, due to steric hindrance, and avoids the introduction of large amounts of mobile alkali metal ions. A combination of glycol ether solvents, ketal solvents, and methyl nylonate provides enhanced dissolution and stripping effects; a protective agent provides efficient protection for the wiring film; and a β-cyclodextrin derivative not only wets the photoresist and increases the volume of photoresist decomposition particles, but also extends the stripping solution's storage stability. These combinations work synergistically to improve stripping effectiveness, applicability, and storage stability.

[0035] The preparation method provided by the present invention first mixes the other components evenly and finally adds the protective agent to prevent the protective agent from being added too early and affecting the dispersion and dissolution of other components. The preparation method improves the stability of the stripping liquid composition by setting the raw material mixing order and the filtration step.

[0036] The application of the stripping liquid composition provided by the present invention, in view of the advantages of the above-mentioned stripping liquid composition, can meet the needs of different metal films in the photoresist removal process, improve the accuracy, reliability and service life of high-resolution and high-refresh rate display panels, and promote the development of downstream industries. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0038] Hereinafter, the terms "including", "having" and their cognates, which may be used in various embodiments of the present invention, are intended only to indicate specific features, numbers, steps, operations, elements, components or combinations of the foregoing items, and should not be understood as first excluding the existence of one or more other features, numbers, steps, operations, elements, components or combinations of the foregoing items or the possibility of adding one or more features, numbers, steps, operations, elements, components or combinations of the foregoing items.

[0039] The first aspect of the present invention provides a stripping solution composition comprising an organic base, a glycol ether solvent, a ketal solvent, methyl nylonate, a protective agent, a β-cyclodextrin derivative and pure water; the organic base comprises a hindered alcoholamine and a bicyclic guanidine compound.

[0040] The stripping solution composition provided by the present invention acts on the photoresist through a combination of hindered alcohol amines and bicyclic guanidine compounds, which can effectively destroy the macromolecular structure of the photoresist. The hindered alcohol amines are less corrosive than other strong bases such as non-hindered alcohol amines due to the steric hindrance effect, and also avoid the introduction of a large number of mobile alkali metal ions. The combination of glycol ether solvents, ketal solvents and methyl nylonate provides better dissolution and stripping effects; the protective agent achieves efficient protection of the wiring film; the β-cyclodextrin derivative can not only wet the photoresist and increase the volume of the photoresist decomposition particles, but also prolong the storage stability of the stripping solution. The above-mentioned combinations work together to quickly strip and remove the photoresist on different metal film layers without damaging the bottom metal film layer, and have the effects of long service life and high stripping stability.

[0041] Specifically, hindered alcoholamines, through hydrolysis or direct penetration, can disrupt intermolecular forces, ester bonds, and amide bonds within the photoresist film, thereby promoting its decomposition. Bicyclic guanidine compounds, with their enhanced permeability and nucleophilicity, can penetrate deep into the photoresist's internal structure, severing and disrupting its macromolecular network and dense structure, converting it into more soluble small molecule fragments. The synergistic effect of these two components can cover a wide range of pH values and reactivity, enabling efficient stripping of a wide range of photoresists while reducing prolonged corrosion to the substrate.

[0042] Furthermore, the stripping solution composition includes 7-23 wt% of an organic base, 15-65 wt% of a glycol ether solvent, 15-55 wt% of a ketal solvent, 2-10 wt% of methyl nylonate, 0.5-4.5 wt% of a protective agent, 0.4-5 wt% of a β-cyclodextrin derivative, and the balance is pure water.

[0043] Typically but not limitatively, the organic base content can be, for example, 7wt%, 10wt%, 13wt%, 16wt%, 20wt% or 23wt%, or any value within the range of 7wt% to 23wt%; the methyl nylonate content can be, for example, 2wt%, 4wt%, 6wt%, 8wt% or 10wt%, or any value within the range of 2wt% to 10wt%; the protective agent content can be, for example, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 3wt%, 4wt% or 4.5wt%, or any value within the range of 0.5wt% to 4.5wt%; the β-cyclodextrin derivative content can be, for example, 0.4wt%, 1wt%, 2wt%, 3wt%, 4wt% or 5wt%, or any value within the range of 0.4wt% to 5wt%; the remainder is composed of pure water to ensure that the total mass percentage of the composition is 100%.

[0044] In some optional embodiments, the weight percentage of the organic base is 7% to 23%. When the weight percentage is less than 7%, the stripping effect and rate of the stripping solution will be affected, and the risk of residual photoresist on the substrate will also increase. When the weight percentage is higher than 23%, the proportion of glycol ether solvents and ketal solvents in the photoresist is reduced, which will also affect the stripping effect and stability of the photoresist and may also increase corrosion damage to the wiring film.

[0045] Furthermore, when the organic base content is 7-13wt%, the usage ratio of the bicyclic guanidine compound to the hindered alcoholamine is 0.18-12; when the organic base content is 13-23wt% (excluding 13wt%), the usage ratio of the bicyclic guanidine compound to the hindered alcoholamine is 0.095-6.

[0046] Bicyclic guanidine compounds are a class of strong organic bases, while hindered amines are a class of medium-strength organic bases that also contain hydroxyl (-OH) groups. While their alkalinity is weaker than that of bicyclic guanidine compounds and their solubility is relatively mild, their hydroxyl groups impart good water solubility, solubility enhancement, and some metal corrosion inhibition. The stripping ability of a stripping solution primarily depends on the strong base bicyclic guanidine compounds, but bicyclic guanidine compounds are more corrosive than hindered amines. While hindered amines alone lack sufficient stripping ability, they help reduce corrosiveness and provide auxiliary solubility. Therefore, regulating the total base concentration and the bicyclic guanidine / hindered amine ratio can balance the stripping ability, photoresist dissolution, and coating corrosion protection of the stripping solution.

[0047] Typically but not limitatively, when the organic base content is 7-13 wt %, the ratio of the bicyclic guanidine compound to the hindered alcoholamine can be, for example, 0.18, 0.5, 1, 2, 4, 6, 8, 10 or 12, or any value within the range of 0.18-12.

[0048] When the organic base content is 13 (excluding 13) to 23 wt %, the usage ratio of the bicyclic guanidine compound to the hindered alcoholamine can be, for example, 0.095, 0.2, 0.5, 1, 2, 3, 4, 5 or 6, or any value within the range of 0.095 to 6.

[0049] Furthermore, the hindered alcoholamine is selected from at least one of 2-amino-2-methyl-1-propanol, N,N-diethylethanolamine, N,N-dimethylethanolamine, and 2-amino-2-ethyl-1,3-propanediol.

[0050] Preferably, the bicyclic guanidine compound is at least one selected from 1,5-diazabicyclo[4.3.0]non-5-ene and its derivatives, and 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0051] Glycol ether solvents are primarily used to swell and soften photoresists, facilitating their stripping from the substrate. Ketal solvents, on the other hand, are environmentally friendly. Ketal solvents primarily treat photoresists through wetting and dissolving them, enhancing the ability of organic bases to quickly penetrate the photoresist's interior. They also work synergistically with glycol ether solvents to improve the stripping rate and effectiveness of photoresist stripping.

[0052] Preferably, the glycol ether solvent is at least one of diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monobutyl ether.

[0053] Preferably, the ketal solvent is at least one of acetone glycerol acetal, butanone glycerol acetal and cyclohexanone glycerol acetal.

[0054] Furthermore, the nylon acid methyl ester includes nylon acid dimethyl ester and / or mixed dibasic acid dimethyl ester.

[0055] Methyl nylonate effectively swells and dissolves photoresist components, disrupting the adhesion between the photoresist and the substrate. When used in conjunction with glycol ether and ketal solvents, it significantly enhances photoresist stripping. Dimethyl nylonate increases the amount of photoresist dissolved in the stripper and the stripping rate, thereby extending the lifespan of the stripper. However, if methyl nylonate exceeds 10wt% of the stripper composition, it can affect subsequent water rinsing and replacement performance.

[0056] Preferably, the protective agent comprises an imidazoline compound and / or a sugar amine compound.

[0057] Imidazoline compounds contain hydrophilic groups such as hydroxyl groups and hydrophobic long-chain alkyl structures. The hydrophobic long-chain alkyl structure can form a protective film on the metal surface, effectively preventing stripping fluids from eroding the wiring film layer. The hydrophilic group can be adsorbed on the metal surface through chemical bonds, thereby improving adsorption stability. The amino and / or hydroxyl groups in glycosamine compounds can form chemical bonds with the metal surface, complementing the imidazoline compounds to enhance the density of the protective film and jointly build a reinforced protective layer on the metal surface. Furthermore, glycosamine compounds have reducing and complexing properties, effectively inhibiting the oxidation process of metals.

[0058] Preferably, the imidazoline compound includes at least one of octyl hydroxyethyl imidazoline, 2-tridecyl-1-aminoethyl imidazoline, coconut oil hydroxyethyl imidazoline, lauryl hydroxyethyl imidazoline, and 2-undecyl-N-carboxymethyl-N-hydroxyethyl imidazoline.

[0059] Preferably, the sugar amine compound includes at least one of 1-amino-1-deoxy-β-D-galactose, 1-amino-2,5-anhydro-1-deoxy-D-mannitol, 1-deoxy-1-amino-β-glucose, 1-amino-β-D-galactose, and β-D-mannosylamine.

[0060] Preferably, the protective agent comprises an imidazoline compound and a sugar amine compound in a mass ratio of (0.4-6):1.

[0061] Typically but not limitatively, the mass ratio of the imidazoline compound to the sugar amine compound in the protective agent can be, for example, 0.4:1, 1:1, 2:1, 3:1, 4:1, 5:1 or 6:1, or any value within the range of 0.4 to 6:1.

[0062] Preferably, the β-cyclodextrin derivative includes at least one of hydroxyethyl-β-cyclodextrin, hydroxypropyl-β-cyclodextrin, carboxymethyl-β-cyclodextrin, mono-(6-amino-6-deoxy)-β-cyclodextrin, and mono-(6-mercapto-6-deoxy)-β-cyclodextrin.

[0063] β-cyclodextrin derivatives, with their unique cyclic cavity structure, can effectively encapsulate photoresist fragments and hydrophobic components, thereby wetting the photoresist and increasing the volume of photoresist decomposition particles. Furthermore, β-cyclodextrin derivatives can form host-guest complexes with organic bases or protective agents. These complexes can slow the volatilization or decomposition of active ingredients, significantly extending the storage stability of the stripping solution. However, when the β-cyclodextrin derivative dosage exceeds 5wt%, the system viscosity increases significantly, negatively affecting the photoresist stripping efficiency.

[0064] Preferably, the pure water comprises ultrapure water.

[0065] The second aspect of the present invention provides a method for preparing the stripping liquid composition, which comprises first uniformly mixing an organic base, a glycol ether solvent, a ketal solvent, methyl nylonate, a β-cyclodextrin derivative and pure water, and finally adding a protective agent, mixing uniformly and filtering to obtain the stripping liquid composition.

[0066] The preparation method provided by the present invention first mixes the other components evenly and finally adds the protective agent to prevent the protective agent from being added too early and affecting the dispersion and dissolution of other components. The preparation method improves the stability of the stripping liquid composition by setting the raw material mixing order and the filtration step.

[0067] Furthermore, the filtration is divided into primary filtration and secondary filtration.

[0068] Preferably, the filter mesh used in the first-stage filtration has a pore size of 0.45 μm.

[0069] Preferably, the filter mesh used for the secondary filtration has a pore size of 0.1 μm.

[0070] The third aspect of the present invention provides the use of the stripping solution composition in removing photoresist on a metal film.

[0071] The application of the stripping liquid composition provided by the present invention, in view of the advantages of the above-mentioned stripping liquid composition, can meet the needs of different metal films in the photoresist removal process, improve the accuracy, reliability and service life of high-resolution and high-refresh rate display panels, and promote the development of downstream industries.

[0072] Furthermore, the metal film includes a molybdenum film, an aluminum film, a copper film or a silver film; Preferably, the molybdenum-based film includes a pure molybdenum film or a molybdenum-niobium film.

[0073] Preferably, the aluminum-based film includes aluminum / molybdenum film, aluminum / molybdenum-niobium film, aluminum-neodymium-molybdenum film, molybdenum / aluminum / molybdenum film, molybdenum-niobium / aluminum film, molybdenum / aluminum-neodymium film, aluminum / titanium film or titanium / aluminum / titanium film.

[0074] Preferably, the copper-based film includes copper film, copper / molybdenum film, copper / molybdenum niobium film, copper / molybdenum titanium film, copper / molybdenum titanium nickel film, molybdenum titanium nickel / copper / molybdenum titanium nickel film, molybdenum titanium nickel / copper / molybdenum titanium film or molybdenum niobium / copper / molybdenum titanium nickel film.

[0075] Preferably, the silver-based film includes a silver film, an indium tin oxide / silver film, or an indium tin oxide / silver / indium tin oxide film.

[0076] It should be noted that the above “ / ” is used to distinguish two adjacent layers. For example, the aluminum / molybdenum film has a two-layer structure, including a bottom aluminum layer and a molybdenum layer located thereon, which together constitute the aluminum / molybdenum film; similarly, the molybdenum / aluminum-neodymium film also has a two-layer structure, including a bottom molybdenum layer and an aluminum-neodymium alloy layer located thereon, which together constitute the molybdenum / aluminum-neodymium film.

[0077] In the manufacturing process of thin-film transistor liquid crystal displays (TFT-LCDs) and organic light-emitting diode displays (OLEDs), the application of photoresist stripping or cleaning removal is mainly concentrated in the post-etching process of electrode and wiring materials. Specifically, this application involves removing the residual photoresist by stripping or cleaning after the etching process of electrodes and wiring materials is completed to ensure that subsequent process steps can proceed smoothly while maintaining device performance and quality.

[0078] The present invention is further illustrated below by specific examples and comparative examples. However, it should be understood that these examples are merely for the purpose of further explanation and should not be construed as limiting the present invention in any form. The raw materials used in the examples and comparative examples of the present invention, unless otherwise specified, were prepared under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments used without manufacturer's indication are all commercially available conventional products.

[0079] The following is the correspondence between the English and Chinese abbreviations and the specific substances in this invention: AMP─2-amino-2-methyl-1-propanol; DMEA─N,N-dimethylethanolamine; DBN─1,5-diazabicyclo[4.3.0]non-5-ene; DBU─1,8-diazabicyclo[5.4.0]undec-7-ene; BDG─diethylene glycol monobutyl ether; DPM─dipropylene glycol monomethyl ether; ACM─glycerol acetone acetal; DBE─methyl nylonate; CHEI─octylhydroxyethylimidazoline; T1─1-amino-1-deoxy-β-D-galactose; HE-β-CD─hydroxyethyl-β-cyclodextrin; CM-β-CD─carboxymethyl-β-cyclodextrin.

[0080] The formulations of the various embodiments are shown in Table 1 below.

[0081] Table 1

[0082] The formulations of the comparative examples are shown in Table 2 below.

[0083] Table 2

[0084] Comparative Example 15 The difference between this comparative example and Example 1 is that an equal amount of DBN is replaced by sodium hydroxide, and the other components remain unchanged.

[0085] The stripping liquid compositions of the above examples and comparative examples were prepared according to the following method: 1. Start stirring and add ultrapure water, glycol ether solvent, ketal solvent, methyl nylonate and β-cyclodextrin derivative into the liquid preparation tank in sequence. Then maintain the tank liquid temperature in the range of 20-40°C and continue mixing and stirring for 1 hour to obtain a mixture.

[0086] 2. Add the sugar amine compound and the imidazoline compound to the mixture and stir for 30-50 minutes. After fully mixing, perform double-stage precision filtration using PTFE or PP filters with pore sizes of 0.45 μm and 0.1 μm respectively to obtain a stripping liquid composition product.

[0087] Test Example 1: Peeling Ability Test A 4cm x 4cm aluminum / molybdenum substrate was cleaned with acetone and high-purity water for 3-5 minutes each, then dried with high-purity nitrogen. A 2μm thick layer of photoresist was then applied to the aluminum / molybdenum substrate and dried in a 120°C oven for 10 minutes to produce a peelable aluminum / molybdenum substrate test piece.

[0088] The peeling test pieces of the copper / molybdenum plated substrate and the peeling test pieces of the molybdenum plated substrate were prepared according to the above method.

[0089] The stripping test piece was immersed in a stripping liquid composition at a temperature of 45°C for stripping for 2 minutes. After stripping, it was rinsed with high-pressure water for 2 minutes and further dried with high-purity nitrogen. The degree of photoresist residue on the substrate surface after stripping was observed under a microscope, and the results are statistically summarized in Table 3.

[0090] The evaluation criteria for stripping ability are as follows: △-no residue was observed on the substrate, completely removed; ▲- There are traces of photoresist residue on the substrate that is less than 15% of the area; ※-There are traces of photoresist residue on the substrate that are greater than 15% but less than 30% of the area; ╳-The substrate has residual photoresist traces covering more than 30% of the area.

[0091] Test Example 2: Corrosion Test The aluminum / molybdenum-coated substrate cut into a size of 4 cm×4 cm was cleaned with acetone and high-purity water for 3-5 minutes respectively, and then taken out and blown dry with high-purity nitrogen gas for use to obtain the aluminum / molybdenum-coated substrate to be tested.

[0092] The copper / molybdenum plated substrate and molybdenum plated substrate to be tested were prepared according to the above method.

[0093] The substrate was immersed in the stripping solution composition at a temperature of 45°C for 20 minutes. After immersion, it was rinsed with high-pressure water for 2 minutes and further dried with high-purity nitrogen. The change in the coating layer thickness before and after immersion was observed and measured using a scanning electron microscope. The change rate of the coating layer (Å / min) was obtained by dividing it by the immersion time and recorded in Table 3.

[0094] Corrosion resistance rating: ◇-The coating layer change rate is ≤10 Å / min, and the corrosion resistance is good; -10Å / min<Coating layer change rate≤30Å / min, average corrosion resistance; ※-30 Å / min<Coating layer change rate≤60Å / min, corrosion resistance is poor; ╳-The coating layer change rate is greater than 60 Å / min, and the corrosion resistance is poor.

[0095] Test Example 3: Solubility Test RD-PFS120B photoresist (produced by Shenzhen Rongda Photosensitive Technology Co., Ltd.) was baked at 100° C. for 6 hours to obtain a photoresist block, which was then ground in an agate crucible to obtain photoresist powder.

[0096] 4.5g of photoresist powder was dissolved in the 45°C stripper composition, stirred and dissolved for 1 hour. The solution was then vacuum filtered and collected on filter paper. The filter paper was vacuum dried at 80°C for 1 hour and weighed. The photoresist solubility of the stripper composition was calculated and recorded in Table 3.

[0097] The calculation method of photoresist solubility is: S=[1-(m2-m1) / 4.5]×100%, where S represents the solubility of photoresist; m1 and m2 represent the weight of filter paper before filtration and after filtration and drying, respectively.

[0098] The calculated data are recorded in Table 3.

[0099] The evaluation criteria for photoresist dissolution ability are as follows: ○-S≥96%, good solubility; ☉-92%≤S<96%, average solubility; ●-88%≤S<92%, poor solubility; ╳- S<88%, poor solubility.

[0100] Table 3

[0101] Test Example 4: Stability Test The stripping solution compositions of Examples 2, 8, and 9 and Comparative Examples 10, 11, 12, and 14 were heated in a 65°C water bath for 3 and 6 hours, respectively, and then removed for use. The stripping and dissolution capabilities of the heat-treated stripping solution compositions were evaluated using the same methods as in Test Examples 1 and 3, respectively. The results are reported in Table 4.

[0102] Table 4

[0103] As shown in Table 3, the stripping solution compositions prepared in Examples 1-12 were able to completely remove photoresist from the surfaces of the three substrates and exhibited excellent protection for all three substrates, with corrosion rates ≤10 Å / min. Comparative Example 1, which had a low organic base content, and Comparative Example 2, in which the ratio of the bicyclic guanidine compound to the hindered alcohol amine in the organic base was outside the specified range, both showed significant reductions in stripping and dissolving abilities. Comparative Examples 3 and 4, when using either bicyclic guanidine compounds or hindered alcohol amines alone, experienced accelerated corrosion of the underlying metal film or decreased photoresist dissolving ability. Comparative Examples 5, 6, and 7, which did not contain either imidazoline compounds or sugar amine compounds, showed varying degrees of increased corrosion rates for the three metal-coated substrates. Comparative Example 8, due to the absence of a glycol ether solvent, exhibited insufficient photoresist stripping ability, resulting in incomplete cleaning and decreased dissolving ability.

[0104] Comparative Example 9, compared to Example 12, and Comparative Example 13, compared to Example 11, showed a decrease in photoresist solubility and a shortened stripper life due to the omission of the methyl nylonate solvent. Combining the results in Tables 3 and 4, it can be seen that compared to Examples 8 and 9, Comparative Examples 10 and 11 showed a decrease in both solubility and stripper stability due to the lack of or absence of the β-cyclodextrin derivative. Similar results were observed in Example 2 and Comparative Example 12. Comparative Example 14, which further removed the methyl nylonate solvent component from Comparative Example 12, showed further decreases in stripper ability and stripper stability. Compared to Example 1, Comparative Example 15 replaced the bicyclic guanidine compound component with the inorganic base sodium hydroxide, significantly increasing the stripper composition's aggressiveness against the three substrates, failing to achieve the desired results.

[0105] Finally, it should be noted that the above-described embodiments are only specific implementations of the present invention, which are used to illustrate the technical solutions of the present invention, rather than to limit them. The scope of protection of the present invention is not limited thereto. Although the present invention has been described in detail with reference to the above-described embodiments, those skilled in the art should understand that any person skilled in the art can modify or easily conceive of changes to the technical solutions described in the above-described embodiments within the technical scope disclosed by the present invention, or replace some of the technical features therein with equivalents. Such modifications, changes, or replacements do not deviate from the spirit and scope of the technical solutions of the embodiments of the present invention, and should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A stripping liquid composition, characterized in that Including organic base, glycol ether solvent, ketal solvent, methyl nylonate, protective agent, β-cyclodextrin derivative and pure water; The organic base includes hindered alcohol amine and bicyclic guanidine compound.

2. The stripping liquid composition according to claim 1, wherein The invention comprises 7-23 wt% of an organic base, 15-65 wt% of a glycol ether solvent, 15-55 wt% of a ketal solvent, 2-10 wt% of methyl nylonate, 0.5-4.5 wt% of a protective agent, 0.4-5 wt% of a beta-cyclodextrin derivative, and the balance being pure water.

3. The stripping liquid composition according to claim 1, wherein When the content of the organic base is 7-13 wt %, the ratio of the bicyclic guanidine compound to the hindered alcoholamine is 0.18-12; Preferably, when the content of the organic base is 13-23 wt % (excluding 13 wt %), the usage ratio of the bicyclic guanidine compound to the hindered alcoholamine is 0.095-6.

4. The stripping liquid composition according to any one of claims 1 to 3, characterized in that The hindered alcoholamine is selected from at least one of 2-amino-2-methyl-1-propanol, N,N-diethylethanolamine, N,N-dimethylethanolamine, and 2-amino-2-ethyl-1,3-propanediol; Preferably, the bicyclic guanidine compound is at least one selected from 1,5-diazabicyclo[4.3.0]non-5-ene and its derivatives, and 1,8-diazabicyclo[5.4.0]undec-7-ene.

5. The stripping liquid composition according to any one of claims 1 to 3, characterized in that The glycol ether solvent is at least one of diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monobutyl ether; Preferably, the ketal solvent is at least one of acetone glycerol acetal, butanone glycerol acetal and cyclohexanone glycerol acetal.

6. The stripping liquid composition according to any one of claims 1 to 3, characterized in that The nylon acid methyl ester includes nylon acid dimethyl ester and / or mixed dibasic acid dimethyl ester; Preferably, the protective agent comprises an imidazoline compound and / or a sugar amine compound; Preferably, the imidazoline compound includes at least one of octyl hydroxyethyl imidazoline, 2-tridecyl-1-aminoethyl imidazoline, coconut oil hydroxyethyl imidazoline, lauryl hydroxyethyl imidazoline, and 2-undecyl-N-carboxymethyl-N-hydroxyethyl imidazoline; Preferably, the sugar amine compound includes at least one of 1-amino-1-deoxy-β-D-galactose, 1-amino-2,5-anhydro-1-deoxy-D-mannitol, 1-deoxy-1-amino-β-glucose, 1-amino-β-D-galactose, and β-D-mannosylamine; Preferably, the protective agent comprises an imidazoline compound and a sugar amine compound in a mass ratio of (0.4-6):1; Preferably, the β-cyclodextrin derivative includes at least one of hydroxyethyl-β-cyclodextrin, hydroxypropyl-β-cyclodextrin, carboxymethyl-β-cyclodextrin, mono-(6-amino-6-deoxy)-β-cyclodextrin, and mono-(6-mercapto-6-deoxy)-β-cyclodextrin; Preferably, the pure water comprises ultrapure water.

7. A method for preparing the stripping solution composition according to any one of claims 1 to 6, characterized in that: First, an organic base, a glycol ether solvent, a ketal solvent, methyl nylonate, a beta-cyclodextrin derivative and pure water are mixed evenly, and finally a protective agent is added, mixed evenly and filtered to obtain the stripping liquid composition.

8. The preparation method according to claim 7, characterized in that The filtration is divided into primary filtration and secondary filtration; Preferably, the filter mesh used in the first-stage filtration has a pore size of 0.45 μm; Preferably, the filter mesh used for the secondary filtration has a pore size of 0.1 μm.

9. Use of the stripping solution composition according to any one of claims 1 to 6 in removing photoresist from a metal film.

10. The use according to claim 9, characterized in that The metal film includes a molybdenum film, an aluminum film, a copper film or a silver film; Preferably, the molybdenum-based film includes a pure molybdenum film or a molybdenum-niobium film; Preferably, the aluminum film includes aluminum / molybdenum film, aluminum / molybdenum-niobium film, aluminum-neodymium-molybdenum film, molybdenum / aluminum / molybdenum film, molybdenum-niobium / aluminum film, molybdenum / aluminum-neodymium film, aluminum / titanium film or titanium / aluminum / titanium film; Preferably, the copper-based film includes a copper film, a copper / molybdenum film, a copper / molybdenum-niobium film, a copper / molybdenum-titanium film, a copper / molybdenum-titanium-nickel film, a molybdenum-titanium-nickel / copper ... or a molybdenum-niobium / copper / molybdenum-titanium-nickel film; Preferably, the silver-based film includes a silver film, an indium tin oxide / silver film, or an indium tin oxide / silver / indium tin oxide film.

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