A positive photoresist stripping solution and a method for preparing the same

Abstract

This invention belongs to the field of photoresist technology, specifically disclosing a positive photoresist stripping solution, which, by mass percentage, comprises the following components: 35-60% polar organic solvent, 10-20% organic base, 3-6% metal protectant, 1.5-3% imidazoline derivative, 0.5-2% γ-piperazinylpropylmethyldimethoxysilane, 0.5-2.5% sodium borate, 0.5-1% surfactant, and the balance being water. This invention provides a positive photoresist stripping solution whose components work synergistically, resulting in fast stripping speed, low residual photoresist rate, and good protection of copper substrates.

Description

Technical Field

[0001] This invention belongs to the field of photoresist technology, and particularly relates to a positive photoresist stripping solution and its preparation method. Background Technology

[0002] Positive photoresist (positive photoresist) is a key material in photolithography. When exposed to light of a specific wavelength, the chemical properties of its light-receiving portion change, becoming soluble in the developer, thus enabling the precise transfer of patterns from the photomask to the substrate material. Common positive photoresists contain linear phenolic resins and diazonoquinone photosensitive compounds, which can produce fine patterns and are widely used in semiconductor manufacturing, flat panel displays, microelectromechanical systems (MEMS) and other fields.

[0003] Positive resist stripping solution is a chemical solution used to remove unexposed or unwanted positive resist after photolithography. When the stripping solution comes into contact with a copper substrate, impurities, lattice defects, or different crystal orientations on the substrate surface create microscopic electrochemical inhomogeneities. This results in potential differences between different areas of the copper substrate surface, forming numerous tiny galvanic cells that accelerate copper substrate corrosion. Furthermore, the corrosion products form a loose film on the copper substrate surface, which not only fails to protect the substrate but also hinders the contact between the stripping solution and the positive resist, reducing the stripping efficiency. Simultaneously, corrosion products remain on the copper substrate surface, affecting subsequent processes and consequently impacting the adhesion of metal wiring and leading to poor soldering.

[0004] Chinese invention patent document CN117872693A discloses a positive adhesive stripping solution, a method for preparing the positive adhesive stripping solution, and its application. The positive adhesive stripping solution comprises the following components in the following concentration ratios: 22–28 g / L of an amine compound; 27–33 g / L of a first positive adhesive resin solvent; 22–30 g / L of a second positive adhesive resin solvent; 0.01–8 g / L of additives; and the balance being water. The amine compound includes any one of N,N-diethyl-1,3-propanediamine, N,N-diisopropyl-1,3-propanediamine, diethylenetriamine, and N-(2-hydroxyethyl)ethylenediamine. The first positive adhesive resin solvent is a divalent ester DBE or propylene carbonate; the second positive adhesive resin solvent is 3-methoxy-3-methyl-1-butanol or 2-methyl-2,4-pentanediol. This positive adhesive stripping solution has a fast stripping speed and low residual adhesive rate, but it still cannot effectively protect the copper substrate. Summary of the Invention

[0005] The purpose of this invention is to overcome the above-mentioned problems in the prior art and provide a positive adhesive stripping liquid, in which the components work synergistically, resulting in fast stripping speed, low adhesive residue, and better protection of copper substrates.

[0006] To achieve the above-mentioned technical objectives and effects, the present invention is implemented through the following technical solution:

[0007] In a first aspect, the present invention provides a positive adhesive stripping solution, comprising, by weight percentage: 35-60% polar organic solvent, 10-20% organic base, 3-6% metal protectant, 1.5-3% imidazoline derivative, 0.5-2% γ-piperazinylpropylmethyldimethoxysilane, 0.5-2.5% sodium borate, 0.5-1% surfactant, and the balance being water.

[0008] Further, the polar organic solvent is at least one selected from N-methylformamide, N-methylpyrrolidone, N,N-dimethylformamide, diethylene glycol monomethyl ether, ethylene glycol methyl ether, and dimethyl sulfoxide.

[0009] Further, the organic base is at least one selected from diethylene glycolamine, ethylene glycolamine, diethanolamine, triethanolamine, methyldiethanolamine, and hydroxyethyl ethylenediamine.

[0010] Furthermore, the preparation method of the metal protective agent includes the following steps:

[0011] Step (1): Dissolve cyanuric chloride in acetone, add 2-mercaptobenzothiazole, adjust the pH to 8-9 with sodium hydroxide solution, reflux at 60-70℃ for 8-10 hours, add ice water, stir, filter, and dry to obtain the intermediate.

[0012] Step (2): Add the intermediate to N,N-dimethylformamide, add 1,4-butanediamine aqueous solution dropwise to the reaction system, and after the addition is finished, heat to 90-110℃, stir the reaction for 4-8 hours, cool the reaction system to 30-35℃, filter, wash, dry, recrystallize, filter again, and dry again to obtain the metal protectant.

[0013] Furthermore, the reaction formula for the preparation method of the metal protective agent is as follows:

[0014]

[0015] Further, the ratio of the amounts of cyanuric chloride, 2-mercaptobenzothiazole, 1,4-butanediamine aqueous solution, N,N-dimethylformamide, and acetone is (18.1-18.5)g:(30.5-31.5)g:(11-15)g:(100-200)g:(100-200)g.

[0016] Furthermore, the concentration of the 1,4-butanediamine aqueous solution is 25-35 wt%.

[0017] Furthermore, the imidazoline derivative is at least one selected from lauryl hydroxyethyl imidazoline, heptadecanylaminoethyl imidazoline, undecyl imidazoline, dodecyl hydroxyethyl imidazoline, oleyl hydroxyethyl imidazoline, and heptadecanyl hydroxyethyl imidazoline.

[0018] Furthermore, the mass ratio of the metal protective agent to the imidazoline derivative is (1-3):1.

[0019] Furthermore, the surfactant is at least one selected from nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polyethylene glycol, and octadecylamine polyoxyethylene ether.

[0020] Secondly, the present invention provides a method for preparing a positive rubber release solution, comprising the following steps: according to the positive rubber release solution formula, weighing a polar organic solvent, an organic base, a metal protectant, an imidazoline derivative, γ-piperazinylpropylmethyldimethoxysilane, sodium borate, a surfactant, and water, mixing and dissolving all materials completely, then heating to 40-60°C and stirring until uniform and transparent to obtain the positive rubber release solution.

[0021] Compared with the prior art, the beneficial effects of the present invention are:

[0022] 1. In the positive adhesive stripping solution provided by the present invention, polar organic solvents and organic bases work together to form a cascade effect of "swelling-degradation-dissolution": (a) the organic solvents destroy physical cross-linking, causing the positive adhesive structure to loosen; (b) the organic bases penetrate the cross-linking between weak molecular chains; (c) the small molecule degradation products are further dissolved by the organic solvents, thereby causing the positive adhesive to lose its original structure and properties and successfully detach from the copper substrate.

[0023] 2. In the positive adhesive stripping solution provided by this invention, the nitrogen heterocycle and sulfur atoms in the metal protectant can provide lone pairs of electrons to form coordinate bonds with the empty orbitals on the surface of metallic copper, resulting in chemical adsorption. This allows the metal protectant molecules to adhere tightly to the surface of metallic copper. The molecules are arranged in an orderly manner through van der Waals forces and π-π stacking interactions, forming a continuous protective film with a certain thickness and strength. The protective film isolates the corrosive medium and slows down metal corrosion. Furthermore, the conjugated system of benzene rings and heterocycles can disperse the electron cloud, reduce the electron density on the surface of metallic copper, inhibit the dissolution of copper ions, and protect the metal.

[0024] 3. In the positive adhesive stripping solution provided by the present invention, the nitrogen-containing heterocycles in the imidazoline derivative molecules adsorb onto the surface of metallic copper and can also interact with the metal protectant to synergistically enhance the stability and corrosion resistance of the protective film. At the same time, the imidazoline derivative can reduce the surface tension of the stripping solution, enabling the stripping solution to better wet the positive adhesive and the copper substrate surface, improve the penetration ability of the stripping solution, and promote the penetration of the stripping solution into the interface between the positive adhesive and the substrate, thereby more effectively peeling the positive adhesive off the copper substrate.

[0025] 4. In the positive adhesive stripping solution provided by the present invention, the methoxy group in the γ-piperazinylpropylmethyldimethoxysilane molecule undergoes hydrolysis in water to generate silanol groups, which causes the silane coupling agent to form a silane film on the surface of the copper substrate. The silane film reduces the direct contact area between the positive adhesive and the copper substrate through the steric hindrance effect. At the same time, the piperazine group forms hydrogen bonds with the phenolic hydroxyl group in the positive adhesive, which promotes the swelling and stripping of the positive adhesive. Furthermore, the piperazine group can also interact with other components in the stripping solution to enhance the protection of the copper substrate.

[0026] 5. In the positive adhesive stripping solution provided by the present invention, the molecular structures of the metal protectant and the imidazoline derivative both have large steric hindrance. When forming a protective film on the surface of the copper substrate, molecular gaps will be generated, resulting in some areas not being effectively covered and forming protective blind spots. By adding small molecule sodium borate, it can penetrate and fill these gaps, making the protective film structure more compact and complete, thereby constructing a denser and more stable composite protective film, significantly improving the stripping solution's anti-corrosion effect on the copper substrate. Attached Figure Description

[0027] The accompanying drawings, which are included to provide a further understanding of the invention and form part of this application, illustrate exemplary embodiments of the invention and, together with their description, serve to explain the invention and do not constitute an undue limitation thereof. In the drawings:

[0028] Figure 1 This is an OM image of the sample after peeling with the positive adhesive peeling solution of Example 1 provided by the present invention;

[0029] Figure 2 This is the OM image of the sample after peeling with the positive adhesive peeling solution of Comparative Example 2 provided by the present invention;

[0030] Figure 3 This is the OM image of the sample after peeling with the positive adhesive peeling solution of Comparative Example 4 provided by the present invention;

[0031] Figure 4 These are SEM images of the samples before and after peeling using the positive adhesive peeling solution of Example 1, provided by the present invention. Figure 4 In the image, A is a SEM image of the sample before peeling with the positive adhesive stripping solution of Example 1, and B is a SEM image of the sample after peeling with the positive adhesive stripping solution of Example 1.

[0032] Figure 5 These are SEM images of the samples before and after peeling using the positive adhesive peeling solution of Comparative Example 3, provided by this invention. Figure 5 In the image, A is the SEM image of the sample before peeling with the positive adhesive stripping solution of Comparative Example 3, and B is the SEM image of the sample after peeling with the positive adhesive stripping solution of Comparative Example 3.

[0033] Figure 6 These are SEM images of the samples before and after peeling using the positive adhesive peeling solution of Comparative Example 5, provided by this invention. Figure 6 In the image, A is the SEM image of the sample before peeling with the positive adhesive stripping solution of Comparative Example 5, and B is the SEM image of the sample after peeling with the positive adhesive stripping solution of Comparative Example 5. Detailed Implementation

[0034] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] Preparation Example 1

[0036] This preparation example provides a metal protectant, which is prepared by the following method:

[0037] Step (1) Dissolve 18.1g of cyanuric chloride in 100g of acetone, add 30.5g of 2-mercaptobenzothiazole, adjust the pH to 8 with sodium hydroxide solution, reflux at 60℃ for 10h, add ice water, stir, filter, and dry to obtain 33.7g of intermediate with a purity greater than 99%.

[0038] Step (2) The intermediate obtained in step (1) was added to 100g of N,N-dimethylformamide. 15g (25wt%) of 1,4-butanediamine aqueous solution was added dropwise to the reaction system. After the addition was completed, the temperature was raised to 90℃ and the reaction was stirred for 8h. The reaction system was then cooled to 30℃, filtered, washed with acetone, and dried at 60℃ for 4h. Recrystallization was performed using ethyl acetate and acetone (volume ratio 1:1). After filtration and drying, 28.8g of metal protectant with a purity greater than 99% was obtained.

[0039] Preparation Example 2

[0040] This preparation example provides a metal protectant, which is prepared by the following method:

[0041] Step (1) Dissolve 18.3g of cyanuric chloride in 150g of acetone, add 31.0g of 2-mercaptobenzothiazole, adjust the pH to 8.5 with sodium hydroxide solution, reflux at 65℃ for 9h, add ice water, stir, filter, and dry to obtain 35.5g of intermediate with a purity greater than 99%.

[0042] Step (2) The intermediate obtained in step (1) was added to 150g of N,N-dimethylformamide. 11g (35wt%) of 1,4-butanediamine aqueous solution was added dropwise to the reaction system. After the addition was completed, the temperature was raised to 100℃ and the reaction was stirred for 6h. The reaction system was then cooled to 32℃, filtered, washed with acetone, and dried at 60℃ for 4h. Recrystallization was performed using ethyl acetate and acetone (volume ratio 1:1). After filtration and drying, 30.4g of metal protectant with a purity greater than 99% was obtained.

[0043] Preparation Example 3

[0044] This preparation example provides a metal protectant, which is prepared by the following method:

[0045] Step (1) Dissolve 18.5g of cyanuric chloride in 200g of acetone, add 31.5g of 2-mercaptobenzothiazole, adjust the pH to 9 with sodium hydroxide solution, reflux at 70℃ for 8h, add ice water, stir, filter, and dry to obtain 37.6g of intermediate with a purity of 99%.

[0046] Step (2) The intermediate obtained in step (1) was added to 200g of N,N-dimethylformamide. 14g (30wt%) of 1,4-butanediamine aqueous solution was added dropwise to the reaction system. After the addition was completed, the temperature was raised to 110℃ and the reaction was stirred for 4h. The reaction system was then cooled to 35℃, filtered, washed with acetone, and dried at 60℃ for 4h. Recrystallization was performed using ethyl acetate and acetone (volume ratio 1:1). After filtration and drying, 33.6g of metal protectant with a purity greater than 99% was obtained.

[0047] Example 1

[0048] Example 1 provides a positive adhesive stripping solution and its preparation method, as detailed below:

[0049] A positive adhesive stripping solution, by weight percentage, comprises: 60% polar organic solvent, 10% organic base, 4.5% metal protectant, 1.5% imidazoline derivative, 0.5% γ-piperazinylpropylmethyldimethoxysilane, 0.5% sodium borate, 0.5% surfactant, and the balance being water;

[0050] The polar organic solvent was obtained by mixing N-methylformamide and ethylene glycol methyl ether in a mass ratio of 1:1; the organic base was ethylene glycol amine; the metal protectant was prepared in Preparation Example 1; the imidazoline derivative was lauryl hydroxyethyl imidazoline; and the surfactant was nonylphenol polyoxyethylene ether.

[0051] A method for preparing a positive adhesive stripping solution includes the following steps:

[0052] Weigh each component in the above formula according to the mass percentage, mix and dissolve all materials completely, then heat to 40°C and stir until uniform and transparent to obtain positive adhesive release solution.

[0053] Example 2

[0054] Example 2 provides a positive adhesive stripping solution and its preparation method, as detailed below:

[0055] A positive adhesive stripping solution, by weight percentage, comprises: 45% polar organic solvent, 15% organic base, 3% metal protectant, 3% imidazoline derivative, 1% γ-piperazinylpropylmethyldimethoxysilane, 1.5% sodium borate, 0.8% surfactant, and the balance being water;

[0056] The polar organic solvent is N-methylpyrrolidone; the organic base is triethanolamine; the metal protectant is prepared by Preparation Example 2; the imidazoline derivative is heptadecenylaminoethylimidazoline; and the surfactant is polyethylene glycol.

[0057] A method for preparing a positive adhesive stripping solution includes the following steps:

[0058] Weigh each component in the above formula according to the mass percentage, mix and dissolve all materials completely, then heat to 50°C and stir until uniform and transparent to obtain positive adhesive release solution.

[0059] Example 3

[0060] Example 3 provides a positive adhesive stripping solution and its preparation method, as detailed below:

[0061] A positive adhesive stripping solution, by weight percentage, comprises: 35% polar organic solvent, 20% organic base, 6% metal protectant, 3% imidazoline derivative, 2% γ-piperazinylpropylmethyldimethoxysilane, 2.5% sodium borate, 1% surfactant, and the balance being water;

[0062] The polar organic solvent was obtained by mixing N,N-dimethylformamide and dimethyl sulfoxide in a mass ratio of 2:1; the organic base was diethanolamine; the metal protectant was prepared in Preparation Example 3; the imidazoline derivative was obtained by mixing oleo-based hydroxyethyl imidazoline and heptadecenyl hydroxyethyl imidazoline in a mass ratio of 1:1; and the surfactant was octadecylamine polyoxyethylene ether.

[0063] A method for preparing a positive adhesive stripping solution includes the following steps:

[0064] Weigh each component in the above formula according to the mass percentage, mix and dissolve all materials completely, then heat to 60℃ and stir until uniform and transparent to obtain positive adhesive release solution.

[0065] Example 4

[0066] Example 4 provides a positive adhesive stripping solution and its preparation method, as detailed below:

[0067] A positive adhesive stripping solution, by weight percentage, comprises: 45% polar organic solvent, 20% organic base, 5.5% metal protectant, 3% imidazoline derivative, 0.5% γ-piperazinylpropylmethyldimethoxysilane, 2.5% sodium borate, 1% surfactant, and the balance being water;

[0068] The polar organic solvent is N-methylpyrrolidone; the organic base is methyldiethanolamine; the metal protectant is prepared according to Preparation Example 2; the imidazoline derivative is dodecylhydroxyethylimidazoline; and the surfactant is polyethylene glycol.

[0069] A method for preparing a positive adhesive stripping solution includes the following steps:

[0070] Weigh each component in the above formula according to the mass percentage, mix and dissolve all materials completely, then heat to 40°C and stir until uniform and transparent to obtain positive adhesive release solution.

[0071] Example 5

[0072] Example 5 provides a positive adhesive stripping solution and its preparation method, as detailed below:

[0073] A positive adhesive stripping solution, by weight percentage, comprises: 50% polar organic solvent, 13% organic base, 5% metal protectant, 2% imidazoline derivative, 1% γ-piperazinylpropylmethyldimethoxysilane, 1.5% sodium borate, 0.8% surfactant, and the balance being water;

[0074] The polar organic solvent was obtained by mixing N-methylformamide and dimethyl sulfoxide in a mass ratio of 1:1; the organic base was hydroxyethyl ethylenediamine; the metal protectant was prepared in Preparation Example 3; the imidazoline derivative was undecylimidazoline; and the surfactant was octadecylamine polyoxyethylene ether.

[0075] A method for preparing a positive adhesive stripping solution includes the following steps:

[0076] Weigh each component in the above formula according to the mass percentage, mix and dissolve all materials completely, then heat to 60℃ and stir until uniform and transparent to obtain positive adhesive release solution.

[0077] Comparative Example 1

[0078] Comparative Example 1 provides a positive adhesive stripping solution and its preparation method.

[0079] The difference between Comparative Example 1 and Example 1 is that an equal mass of 2-mercaptobenzothiazole was used to replace the metal protective agent (prepared in Preparation Example 1), as follows:

[0080] A positive adhesive stripping solution, by weight percentage, comprises: 60% polar organic solvent, 10% organic base, 4.5% 2-mercaptobenzothiazole, 1.5% imidazoline derivative, 0.5% γ-piperazinylpropylmethyldimethoxysilane, 0.5% sodium borate, 0.5% surfactant, and the balance being water;

[0081] The polar organic solvent is obtained by mixing N-methylformamide and ethylene glycol methyl ether in a mass ratio of 1:1; the organic base is ethylene glycol amine; the imidazoline derivative is lauryl hydroxyethyl imidazoline; and the surfactant is nonylphenol polyoxyethylene ether.

[0082] A method for preparing a positive adhesive stripping solution includes the following steps:

[0083] Weigh each component in the above formula according to the mass percentage, mix and dissolve all materials completely, then heat to 40°C and stir until uniform and transparent to obtain positive adhesive release solution.

[0084] Comparative Example 2

[0085] Comparative Example 2 provides a positive adhesive stripping solution and its preparation method.

[0086] The difference between Comparative Example 2 and Example 1 is that an equal mass of metal protective agent (prepared in Preparation Example 1) was used to replace the imidazoline derivative, as detailed below:

[0087] A positive adhesive stripping solution, by weight percentage, comprises: 60% polar organic solvent, 10% organic base, 6% metal protectant, 0.5% γ-piperazinylpropylmethyldimethoxysilane, 0.5% sodium borate, 0.5% surfactant, and the balance being water;

[0088] The polar organic solvent was obtained by mixing N-methylformamide and ethylene glycol methyl ether in a mass ratio of 1:1; the organic base was ethylene glycol amine; the metal protectant was prepared in Preparation Example 1; and the surfactant was nonylphenol polyoxyethylene ether.

[0089] A method for preparing a positive adhesive stripping solution includes the following steps:

[0090] Weigh each component in the above formula according to the mass percentage, mix and dissolve all materials completely, then heat to 40°C and stir until uniform and transparent to obtain positive adhesive release solution.

[0091] Comparative Example 3

[0092] Comparative Example 3 provides a positive adhesive stripping solution and its preparation method.

[0093] The difference between Comparative Example 3 and Example 1 is that an imidazoline derivative of equal mass was used to replace the metal protective agent (prepared in Preparation Example 1), as follows:

[0094] A positive adhesive stripping solution, by weight percentage, comprises: 60% polar organic solvent, 10% organic base, 6% imidazoline derivative, 0.5% γ-piperazinylpropylmethyldimethoxysilane, 0.5% sodium borate, 0.5% surfactant, and the balance being water;

[0095] The polar organic solvent is obtained by mixing N-methylformamide and ethylene glycol methyl ether in a mass ratio of 1:1; the organic base is ethylene glycol amine; the imidazoline derivative is lauryl hydroxyethyl imidazoline; and the surfactant is nonylphenol polyoxyethylene ether.

[0096] A method for preparing a positive adhesive stripping solution includes the following steps:

[0097] Weigh each component in the above formula according to the mass percentage, mix and dissolve all materials completely, then heat to 40°C and stir until uniform and transparent to obtain positive adhesive release solution.

[0098] Comparative Example 4

[0099] Comparative Example 4 provides a positive adhesive stripping solution and its preparation method.

[0100] The difference between Comparative Example 4 and Example 1 is that γ-piperazinylpropylmethyldimethoxysilane was not added, as follows:

[0101] A positive adhesive stripping solution, by weight percentage, comprises: 60% polar organic solvent, 10% organic base, 4.5% metal protectant, 1.5% imidazoline derivative, 0.5% sodium borate, 0.5% surfactant, and the balance being water;

[0102] The polar organic solvent was obtained by mixing N-methylformamide and ethylene glycol methyl ether in a mass ratio of 1:1; the organic base was ethylene glycol amine; the metal protectant was prepared in Preparation Example 1; the imidazoline derivative was lauryl hydroxyethyl imidazoline; and the surfactant was nonylphenol polyoxyethylene ether.

[0103] A method for preparing a positive adhesive stripping solution includes the following steps:

[0104] Weigh each component in the above formula according to the mass percentage, mix and dissolve all materials completely, then heat to 40°C and stir until uniform and transparent to obtain positive adhesive release solution.

[0105] Comparative Example 5

[0106] Comparative Example 5 provides a positive adhesive stripping solution and its preparation method.

[0107] The difference between Comparative Example 5 and Example 1 is that sodium borate is not added, as follows:

[0108] A positive adhesive stripping solution, by weight percentage, comprises: 60% polar organic solvent, 10% organic base, 4.5% metal protectant, 1.5% imidazoline derivative, 0.5% γ-piperazinylpropylmethyldimethoxysilane, 0.5% surfactant, and the balance being water;

[0109] The polar organic solvent was obtained by mixing N-methylformamide and ethylene glycol methyl ether in a mass ratio of 1:1; the organic base was ethylene glycol amine; the metal protectant was prepared in Preparation Example 1; the imidazoline derivative was lauryl hydroxyethyl imidazoline; and the surfactant was nonylphenol polyoxyethylene ether.

[0110] A method for preparing a positive adhesive stripping solution includes the following steps:

[0111] Weigh each component in the above formula according to the mass percentage, mix and dissolve all materials completely, then heat to 40°C and stir until uniform and transparent to obtain positive adhesive release solution.

[0112] Performance testing

[0113] The positive adhesive stripping solutions prepared in the examples and comparative examples were used to treat copper substrates containing positive adhesive. The stripping effect of the substrates after stripping was evaluated. The relevant experimental procedures and evaluation parameters are as follows:

[0114] Peeling method: At 60°C, the substrate sample containing positive adhesive is immersed in the positive adhesive peeling solution prepared in the embodiments and comparative examples of the present invention and peeled for 120 seconds, then rinsed with ultrapure water for 1 minute, and finally dried with high-purity nitrogen to obtain the sample after peeling with positive adhesive peeling solution.

[0115] Stripping effect: After cleaning, the surface of the copper substrate sample was observed using an optical microscope (OM) to check for any photoresist residue; the thickness change of the copper film layer was measured using a scanning electron microscope (SEM); and the amount of Cu leached in the stripping solution was measured to evaluate the corrosion of the metal layer.

[0116] The relevant experimental results are shown in Table 1;

[0117] Table 1

[0118]

[0119]

[0120] As can be seen from the table above, the performance of the stripping fluids in Examples 1-5 is significantly better than that in Comparative Examples 1-5.

[0121] OM and SEM images of the samples were collected during the peeling process with the positive adhesive stripping solution. The results are as follows: Figure 1-6 As shown, where Figure 1 The image shows the OM (Organic Image) of the sample after peeling with the positive adhesive stripping solution of Example 1; Figure 2 The OM image of the sample after peeling with the positive adhesive stripping solution of Comparative Example 2; Figure 3 The OM image of the sample after being peeled using the positive adhesive peeling solution of Comparative Example 4; Figure 4 Image A is a SEM image of the sample before peeling with the positive adhesive stripping solution of Example 1, and image B is a SEM image of the sample after peeling with the positive adhesive stripping solution of Example 1. Figure 5 In Figure A, the sample before peeling with the positive adhesive stripping solution of Comparative Example 3 is shown in SEM image, and in Figure B, the sample after peeling with the positive adhesive stripping solution of Comparative Example 3 is shown in SEM image. Figure 6 Image A is a SEM image of the sample before peeling with the positive adhesive stripping solution of Comparative Example 5, and image B is a SEM image of the sample after peeling with the positive adhesive stripping solution of Comparative Example 5.

[0122] comprehensive Figure 1-6 Comparing the data in Table 1 with those in Comparative Example 1, it is shown that the metal protectant prepared in Preparation Example 1, when added to the stripping solution of the present invention, exhibits superior corrosion resistance compared to 2-mercaptobenzothiazole. Comparing Example 1 with Comparative Examples 2 and 3, it is shown that the combined use of the metal protectant and imidazoline derivative in the stripping solution of the present invention not only helps protect the copper substrate but also improves the stripping effect of the stripping solution. Comparing Example 1 with Comparative Example 4, it is shown that the addition of γ-piperazinylpropylmethyldimethoxysilane to the stripping solution of the present invention effectively enhances both the stripping and corrosion resistance effects. Comparing Example 1 with Comparative Example 5, it is shown that the addition of sodium borate to the stripping solution of the present invention, in conjunction with other components, improves the corrosion resistance of the stripping solution.

[0123] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0124] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A positive adhesive stripping liquid, characterized in that, By weight percentage, it includes the following components: 35-60% polar organic solvent, 10-20% organic base, 3-6% metal protectant, 1.5-3% imidazoline derivative, 0.5-2% γ-piperazinylpropylmethyldimethoxysilane, 0.5-2.5% sodium borate, 0.5-1% surfactant, and the balance being water; The preparation method of the metal protective agent includes the following steps: Step (1): Dissolve cyanuric chloride in acetone, add 2-mercaptobenzothiazole, adjust the pH to 8-9 with sodium hydroxide solution, reflux at 60-70℃ for 8-10 hours, add ice water, stir, filter, and dry to obtain the intermediate. Step (2): Add the intermediate to N,N-dimethylformamide, add 1,4-butanediamine aqueous solution dropwise to the reaction system, and after the addition is finished, heat to 90-110℃, stir the reaction for 4-8 hours, cool the reaction system to 30-35℃, and after filtration, washing, drying, recrystallization, filtration again, and drying again, the metal protectant is obtained.

2. The adhesive stripping liquid according to claim 1, characterized in that, The polar organic solvent is at least one of N-methylformamide, N-methylpyrrolidone, N,N-dimethylformamide, diethylene glycol monomethyl ether, ethylene glycol methyl ether, and dimethyl sulfoxide.

3. The adhesive stripping solution according to claim 1, characterized in that, The organic base is at least one of diethylene glycolamine, ethylene glycolamine, diethanolamine, triethanolamine, methyldiethanolamine, and hydroxyethyl ethylenediamine.

4. The adhesive stripping liquid according to claim 1, characterized in that, The ratio of the amounts of cyanuric chloride, 2-mercaptobenzothiazole, 1,4-butanediamine aqueous solution, N,N-dimethylformamide, and acetone is (18.1-18.5) g: (30.5-31.5) g: (11-15) g: (100-200) g: (100-200) g.

5. The adhesive stripping solution according to claim 1, characterized in that, The concentration of the 1,4-butanediamine aqueous solution is 25-35 wt%.

6. The adhesive stripping solution according to claim 1, characterized in that, The imidazoline derivative is at least one selected from lauryl hydroxyethyl imidazoline, heptadecenylaminoethyl imidazoline, undecyl imidazoline, dodecyl hydroxyethyl imidazoline, oleyl hydroxyethyl imidazoline, and heptadecenyl hydroxyethyl imidazoline.

7. The adhesive stripping liquid according to claim 1, characterized in that, The mass ratio of the metal protectant to the imidazoline derivative is (1-3):

1.

8. The adhesive stripping liquid according to claim 1, characterized in that, The surfactant is at least one of nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polyethylene glycol, and octadecylamine polyoxyethylene ether.

9. A method for preparing the positive adhesive stripping liquid according to any one of claims 1-8, characterized in that, The process includes the following steps: According to the formula for positive rubber release solution, weigh out the polar organic solvent, organic base, metal protectant, imidazoline derivative, γ-piperazinylpropylmethyldimethoxysilane, sodium borate, surfactant, and water. Mix and dissolve all materials completely, then heat to 40-60℃ and stir until uniform and transparent to obtain positive rubber release solution.

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