A photoresist composition and preparation method thereof

Abstract

The present invention provides a kind of photoresist composition and preparation method thereof, belong to the field of photoresist technology, comprise the following steps: after acrylate mixed monomer, deionized water, sodium lauryl sulfate and isomeric tridecanol ethoxylate mixture, NaHCO3 solution, dibenzoyl peroxide solution are mixed evenly, stirring reaction, after hexafluorobutyl acrylate monomer and dibenzoyl peroxide solution are slowly dripped, cooling, and fluorine-containing acrylate emulsion is obtained; Polyethylene glycol, toluene diisocyanate and N, N-dimethylformamide are mixed evenly, heated and stirred, citric acid is added and stirred to react, and bio-based polyurethane oligomer is obtained; Fluorine-containing acrylate emulsion, bio-based polyurethane oligomer, magnesium fluoride / riboflavin complex, active diluent are mixed evenly, and photoresist composition is obtained. The present invention can realize bio-based photoinitiator ultraviolet light curing while improving photoresist alkali etching durability and hydrophobicity.

Description

Technical Field

[0001] The invention relates to the technical field of photoresists, and in particular to a photoresist composition and a preparation method thereof. Background Art

[0002] Photoresist (also known as photoresist) refers to an etching-resistant thin film material whose solubility changes through irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, etc. Photoresist is a light-sensitive mixed liquid composed of materials such as resin, photosensitizer, solvent and additives. It has the characteristics of cross-linking curing or degradation reaction under the action of light. Its surface has the ability to resist etching. It needs to play an anti-etching protection role in the photolithography process, so it is used in the field of metal etching.

[0003] The patent document with announcement number CN102653581B provides an alkali-soluble resin and a method for making the same, a photosensitive resin composition, and a photoresist. The molecular structure of the alkali-soluble resin contains a phenolic epoxy acrylate structure to achieve that no heat-resistant resin remains during development, and after the patterning process, the epoxy acrylate group reacts with the carboxyl group, thereby increasing the thermal stability of the photosensitive resin. However, when the photoresist in the prior art comes into contact with an alkaline metal etching solution, the alkaline metal etching solution and the alkali-soluble resin in the photoresist undergo a degradation reaction, causing the photoresist film to be peeled off by the etching solution. Therefore, for metal substrates (such as aluminum substrates) that require alkaline etching treatment, this photoresist cannot provide effective protection. Although this photoresist has good acid resistance, its poor tolerance to alkaline environments limits its applicability in related applications.

[0004] In addition, photoinitiators, as key components of UV-curing systems, can absorb light and generate active free radicals to initiate polymerization. However, due to the disadvantages of low molecular weight photoinitiators, such as odor, yellowing, and poor compatibility with UV-curable resins, they are often regarded as a problem in photopolymerization; in addition, in the synthesis of materials by photopolymerization, the replacement of potentially toxic photoinitiators has attracted increasing attention, and bio-based initiators have been developed as valuable alternatives to overcome their shortcomings and have become a research hotspot.

[0005] Therefore, it is necessary to provide a photoresist composition and a preparation method thereof to solve the problems existing in the above-mentioned prior art. Summary of the invention

[0006] In view of this, the present invention provides a photoresist composition and a preparation method thereof, which can improve the alkali etching durability and hydrophobicity of the photoresist while realizing ultraviolet light curing of a bio-based photoinitiator.

[0007] To achieve the above object, the present invention provides a photoresist composition and a preparation method thereof, comprising the following steps:

[0008] S1, acrylate monomer mixture, deionized water, a mixture of sodium dodecyl sulfate and isomeric tridecanol ethoxylate, NaHCO 3 After the solution and the dibenzoyl peroxide solution are evenly mixed, the mixture is stirred for reaction, and the hexafluorobutyl acrylate monomer and the dibenzoyl peroxide solution are slowly dropped into the mixture, and the mixture is cooled to obtain a fluorinated acrylate emulsion;

[0009] S2, mixing polyethylene glycol, toluene diisocyanate and N,N-dimethylformamide evenly, heating and stirring, adding citric acid and stirring to react, thereby obtaining a bio-based polyurethane oligomer;

[0010] S3. Evenly mix the fluorine-containing acrylic emulsion, the bio-based polyurethane oligomer, the magnesium fluoride / riboflavin complex, and the active diluent to prepare a photoresist composition.

[0011] The present invention prepares a fluorinated acrylic ester emulsion, wherein a mixture of sodium dodecyl sulfate and isomeric tridecanol ethoxylates is used as an emulsifier to improve the stability of the emulsion and reduce aggregation between polymer particles. 3 The solution can neutralize the acidic substances in the system, maintain an appropriate pH range, and help maintain the stability of the emulsion. Benzoyl peroxide solution decomposes under heating conditions to generate free radicals. These free radicals initiate polymerization reactions by attacking the double bonds of the acrylate mixed monomers, thereby polymerizing the monomers into acrylate polymers. Hexafluorobutyl acrylate is a fluorine-containing monomer. Fluorine has the strongest electronegativity and low surface energy. The introduction of hexafluorobutyl acrylate into acrylate polymers makes the fluorinated polymer have lower surface energy, excellent water resistance, and chemical etching resistance. In addition, citric acid is used to replace part of the polyethylene glycol to encapsulate the isocyanate group. The citric acid molecule contains multiple carboxyl groups. These functional groups can complex with the metal surface to form a stable complex, which improves the stability of the metal surface while reducing the number of free metal ions, thereby inhibiting the corrosion process. In addition, citric acid, as a chelating agent, can form multiple complexes with metal ions. This structural characteristic is beneficial to improving the anti-corrosion effect. In the process of preparing a composite emulsion by mixing a bio-based polyurethane oligomer containing citric acid with a fluorinated acrylate emulsion, the oxygen atom in the citric acid carries a lone pair of electrons, which can form a tighter adsorption layer through donor-acceptor interaction. The CF bond of hexafluorobutyl acrylate and the presence of fluorine atoms make it more tightly bonded to the metal surface. The combination of the two can construct a denser and more effective etching-resistant barrier, so that the overall impact resistance, flexibility and adhesion of the polyurethane are retained while the fluorinated acrylate and citric acid give the overall alkaline etching durability.

[0012] In the process of preparing the photoresist composition, the present invention uses a magnesium fluoride / riboflavin complex as a photoinitiator. Fluorine ions in magnesium fluoride are difficult to be replaced or participate in reactions in many chemical reactions, which gives magnesium fluoride strong corrosion resistance. Adding magnesium fluoride into the photoresist composition increases the overall chemical etching resistance and further improves the alkali resistance. Riboflavin exists in plants and animals and has strong blue light and ultraviolet absorption capabilities. It can be used as a bio-based photoinitiator, absorbs ultraviolet light and is excited to a high energy state, and further promotes the generation of free radicals through energy transfer. These free radicals can initiate the polymerization reaction of acrylate monomers, thereby promoting the polymerization process under ultraviolet light irradiation.

[0013] Optionally, the acrylic acid ester mixed monomer in step S1 is a mixture of butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate and methacrylic acid, wherein the mass fraction ratio of butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate and methacrylic acid is 1:1:1:1; the mass fraction ratio of sodium dodecyl sulfate to the volume fraction of isomeric tridecanol ethoxylate is 1:1, and NaHCO 3 The mass concentration of the solution is 0.25%, and the mass concentration of the benzoyl peroxide solution is 10%.

[0014] Optionally, in step S1, the reaction is stirred at 75-80° C. at a stirring speed of 300 r / min for 2-3 hours, the hexafluorobutyl acrylate monomer and the dibenzoyl peroxide solution are slowly dripped into the mixed system under stirring within 3 hours, the mixture is cooled to 20-35° C., and 2-amino-2-methyl-1-propanol solution is added to neutralize the pH to 7.0-8.0 to obtain a fluorine-containing acrylate emulsion.

[0015] Optionally, castor oil is added into step S2, mixed evenly with polyethylene glycol, toluene diisocyanate and N,N-dimethylformamide, and heated and stirred at 55-65° C. for 5-7 hours.

[0016] The invention utilizes castor oil to replace part of polyethylene glycol, and polymerizes the hydroxyl groups in the long fatty chains of castor oil with isocyanate groups, wherein the long fatty chains enable the cured product to have excellent flexibility and etching resistance.

[0017] Optionally, after adding citric acid in step S2 and stirring the mixture for 3 to 5 hours, glucose is further added and stirred for 2 to 4 hours to finally obtain a bio-based polyurethane oligomer.

[0018] The present invention also adds glucose in the process of preparing the bio-based polyurethane oligomer. The glucose molecule contains multiple hydroxyl groups, which can undergo physical or chemical adsorption with the metal surface, thereby effectively isolating the contact between moisture, oxygen or other corrosive substances and the metal surface, further reducing the corrosion rate of the metal, and cooperating with citric acid to form a more complete protective layer. In addition, the reducing effect of glucose can help reduce the formation of oxides, thereby delaying the corrosion process and further improving etching durability.

[0019] Optionally, in step S3, the magnesium fluoride / riboflavin complex is prepared by mixing a riboflavin suspension and a magnesium fluoride suspension, adding 3-aminopropyltriethoxysilane, stirring and mixing, adding acetic acid solution to adjust the pH value to 4.0-5.0, reacting at 40-50° C. for 4-6 hours, and drying at 50° C. for 2-4 hours to obtain the magnesium fluoride / riboflavin complex.

[0020] The present invention adds 3-aminopropyltriethoxysilane as a coupling agent in the preparation of the magnesium fluoride / riboflavin complex to promote the cross-linking of magnesium fluoride and riboflavin to improve the overall dispersibility of magnesium fluoride.

[0021] Optionally, the mass concentration of the acetic acid solution is 66.7%; the riboflavin suspension is obtained by slowly adding deionized water to riboflavin powder and magnetically stirring for 15 minutes; the magnesium fluoride suspension is obtained by slowly adding deionized water to magnesium fluoride powder and magnetically stirring for 15 minutes.

[0022] Optionally, in step S3, triethanolamine solution is further added and mixed evenly with fluorinated acrylic emulsion, bio-based polyurethane oligomer, magnesium fluoride / riboflavin complex and active diluent; wherein the active diluent is one of phenyl glycidyl ether, diepoxy ethylene glycol diglycidyl ether and resorcinol diglycidyl ether, and the volume concentration of the triethanolamine solution is 20%.

[0023] The invention uses triethanolamine as a co-initiator, and the addition of a small amount of triethanolamine improves the ultraviolet light curing efficiency.

[0024] Optionally, the photoresist composition comprises the following raw materials in parts by weight: 20-30 parts of fluorine-containing acrylate emulsion, 10-15 parts of bio-based polyurethane oligomer, 1-2 parts of magnesium fluoride / riboflavin complex, 0.5-1 parts of 20% triethanolamine solution, and 3-6 parts of active diluent.

[0025] Optionally, the raw materials of the fluorinated acrylic emulsion include 10-20 parts by weight of acrylic acid ester mixed monomer, 50-70 parts by weight of deionized water, 6-12 parts by weight of a mixture of sodium dodecyl sulfate and isomeric tridecanol ethoxylates, and NaHCO 3solution 0.5-1 parts, dibenzoyl peroxide solution 1.3-2.5 parts; the raw materials of the magnesium fluoride / riboflavin complex include 30 parts of riboflavin suspension calculated by volume, 20 parts of magnesium fluoride suspension, and 1.2 parts of 3-aminopropyltriethoxysilane; the raw materials of the bio-based polyurethane include 5 parts of polyethylene glycol calculated by weight, 2 parts of castor oil, 10 parts of toluene diisocyanate, 30 parts of N,N-dimethylformamide, 3-5 parts of citric acid, and 2-5 parts of glucose.

[0026] The above technical solution of the present invention includes at least the following beneficial effects:

[0027] 1. The present invention prepares a fluorinated acrylic emulsion, and hexafluorobutyl acrylate is used as a fluorinated monomer, so that the fluorinated polymer has low surface free energy, excellent water resistance and chemical etching resistance, and citric acid is used to replace part of polyethylene glycol to encapsulate isocyanate groups. The multiple carboxyl groups contained in the citric acid molecules can be complexed with the metal surface to form a stable complex, which improves the stability of the metal surface while reducing the number of free metal ions, thereby inhibiting the corrosion process and improving the durability of alkali etching.

[0028] 2. In the process of preparing the photoresist composition, the present invention uses a magnesium fluoride / riboflavin complex as a photoinitiator. The fluoride ions in the magnesium fluoride are difficult to be replaced or participate in the reaction in many chemical reactions, which gives the magnesium fluoride a stronger etching resistance and further improves the alkali resistance. Riboflavin, as a bio-based photoinitiator, initiates the polymerization reaction of acrylate monomers by promoting the generation of free radicals, thereby promoting the polymerization process under ultraviolet light irradiation. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The following is a line graph showing the change in photoresist thickness during wet etching experiments performed within 0 to 25 seconds for Examples 1 to 5 of the present invention and Comparative Examples 1 to 3. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical solution and advantages of the embodiment of the present invention clearer, the technical solution of the embodiment of the present invention will be clearly and completely described in combination with the embodiment of the present invention. Obviously, the described embodiment is a part of the embodiment of the present invention, not all the embodiments. Based on the described embodiment of the present invention, all other embodiments obtained by ordinary technicians in this field belong to the scope of protection of the present invention.

[0031] Example 1

[0032] 15 parts of acrylic acid ester mixed monomers were mixed with 60 parts of deionized water, 8 parts of a mixture of sodium dodecyl sulfate and isomeric tridecanol ethoxylate, 0.7 parts of NaHCO with a mass concentration of 0.25%, and 1.5 parts of ethyl acetate. 3After the mixture is uniformly mixed with 1.5 parts of a 10% dibenzoyl peroxide solution, the mixture is stirred at 80°C at a stirring speed of 300 r / min for 2.5 hours, and then 4 parts of hexafluorobutyl acrylate monomer and 0.4 parts of a 10% dibenzoyl peroxide solution are slowly dripped into the mixed system under stirring within 3 hours, and the mixture is cooled to 25°C, and a 3% volume concentration of 2-amino-2-methyl-1-propanol solution is added to neutralize the pH to 7.2 to obtain a fluorinated acrylate emulsion; wherein the mass ratio of butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate and methacrylic acid is 1:1:1:1, and the mass ratio of sodium dodecyl sulfate to the volume ratio of isomeric tridecyl alcohol ethoxylate is 1:1.

[0033] Slowly add 10 parts of deionized water to 4 parts of riboflavin powder, and stir magnetically for 15 minutes to obtain a riboflavin suspension; slowly add 10 parts of deionized water to 20 parts of magnesium fluoride powder, and stir magnetically for 15 minutes to obtain a magnesium fluoride suspension; after mixing 30 parts of riboflavin suspension with 20 parts of magnesium fluoride suspension, add 1.2 parts of 3-aminopropyltriethoxysilane, stir for 15 minutes to mix, slowly add 66.7% acetic acid solution dropwise to the solution, adjust the pH value to 4.7, react at 40-50°C for 5 hours, and dry at 50°C for 3 hours to obtain a magnesium fluoride / riboflavin complex.

[0034] 5 parts of polyethylene glycol, 2 parts of castor oil, 10 parts of toluene diisocyanate and 30 parts of N, N-dimethylformamide were mixed evenly and heated and stirred at 60°C for 6 hours. 3-5 parts of citric acid were added and stirred for 4 hours, and then 4 parts of glucose were added and stirred for 3 hours to obtain a bio-based polyurethane oligomer.

[0035] A photoresist composition was prepared by uniformly mixing 25 parts of fluorine-containing acrylic emulsion, 12 parts of bio-based polyurethane oligomer, 1.5 parts of magnesium fluoride / riboflavin complex, 0.6 parts of triethanolamine solution with a volume concentration of 20%, and 5 parts of phenyl glycidyl ether.

[0036] Example 2

[0037] 10 parts of acrylic acid ester mixed monomers were mixed with 50 parts of deionized water, 6 parts of a mixture of sodium dodecyl sulfate and isomeric tridecanol ethoxylate, and 0.5 parts of a 0.25% mass concentration of NaHCO 3After the mixture is uniformly mixed with a 10% mass concentration dibenzoyl peroxide solution, the mixture is stirred at 75°C at a stirring speed of 300 r / min for 2 hours, and then 3 parts of hexafluorobutyl acrylate monomer and 0.3 parts of 10% mass concentration dibenzoyl peroxide solution are slowly dripped into the mixed system under stirring within 3 hours, and the mixture is cooled to 20°C, and a 3% volume concentration of 2-amino-2-methyl-1-propanol solution is added to neutralize the pH to 7.0 to obtain a fluorinated acrylate emulsion; wherein the mass ratio of butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate and methacrylic acid is 1:1:1:1, and the mass ratio of sodium dodecyl sulfate to the volume ratio of isomeric tridecyl alcohol ethoxylate is 1:1.

[0038] Slowly add 10 parts of deionized water to 4 parts of riboflavin powder, and stir magnetically for 15 minutes to obtain a riboflavin suspension; slowly add 10 parts of deionized water to 20 parts of magnesium fluoride powder, and stir magnetically for 15 minutes to obtain a magnesium fluoride suspension; after mixing 30 parts of riboflavin suspension with 20 parts of magnesium fluoride suspension, add 1.2 parts of 3-aminopropyltriethoxysilane, stir for 15 minutes to mix, slowly add acetic acid solution with a mass concentration of 66.7% to the solution, adjust the pH value to 4.0, react at 40°C for 4 hours, and dry at 50°C for 2 hours to obtain a magnesium fluoride / riboflavin complex.

[0039] 5 parts of polyethylene glycol, 2 parts of castor oil, 10 parts of toluene diisocyanate and 30 parts of N, N-dimethylformamide were mixed evenly and heated and stirred at 55°C for 5 hours. 3 parts of citric acid were added and stirred for 3 hours, and then 2 parts of glucose were added and stirred for 2 hours to obtain a bio-based polyurethane oligomer.

[0040] The photoresist composition was prepared by uniformly mixing 20 parts of fluorine-containing acrylic emulsion, 10 parts of bio-based polyurethane oligomer, 1 part of magnesium fluoride / riboflavin complex, 0.5 parts of triethanolamine solution with a volume concentration of 20%, and 3 parts of ethylene glycol diglycidyl ether with a diepoxy group.

[0041] Example 3

[0042] 20 parts of acrylic acid ester mixed monomers were mixed with 70 parts of deionized water, 12 parts of a mixture of sodium dodecyl sulfate and isomeric tridecanol ethoxylate, and 1 part of a 0.25% mass concentration of NaHCO 3After the solution and 2 parts of 10% dibenzoyl peroxide solution are evenly mixed, the mixture is stirred at 80°C at a stirring speed of 300r / min for 3h, and then 5 parts of hexafluorobutyl acrylate monomer and 0.5 parts of 10% dibenzoyl peroxide solution are slowly dripped into the mixed system under stirring within 3h, and the mixture is cooled to 35°C, and 3% volume concentration of 2-amino-2-methyl-1-propanol solution is added to neutralize the pH to 8.0 to obtain a fluorine-containing acrylate emulsion; wherein the mass ratio of butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate and methacrylic acid is 1:1:1:1, and the mass ratio of sodium dodecyl sulfate to the volume ratio of isomeric tridecyl alcohol ethoxylate is 1:1.

[0043] Slowly add 10 parts of deionized water to 4 parts of riboflavin powder, and stir magnetically for 15 minutes to obtain a riboflavin suspension; slowly add 10 parts of deionized water to 20 parts of magnesium fluoride powder, and stir magnetically for 15 minutes to obtain a magnesium fluoride suspension; after mixing 30 parts of riboflavin suspension with 20 parts of magnesium fluoride suspension, add 1.2 parts of 3-aminopropyltriethoxysilane, stir for 15 minutes to mix, slowly add acetic acid solution with a mass concentration of 66.7% to the solution, adjust the pH value to 5.0, react at 50°C for 6 hours, and dry at 50°C for 4 hours to obtain a magnesium fluoride / riboflavin complex.

[0044] 5 parts of polyethylene glycol, 2 parts of castor oil, 10 parts of toluene diisocyanate and 30 parts of N, N-dimethylformamide were mixed evenly and heated and stirred at 65°C for 7 hours. 5 parts of citric acid were added and stirred for 5 hours, and then 5 parts of glucose were added and stirred for 4 hours to obtain a bio-based polyurethane oligomer.

[0045] 30 parts of fluorine-containing acrylic emulsion, 15 parts of bio-based polyurethane oligomer, 1.5 parts of magnesium fluoride / riboflavin complex and 6 parts of resorcinol bisglycidyl ether were uniformly mixed to prepare a photoresist composition.

[0046] Example 4

[0047] 17 parts of acrylic acid ester mixed monomers were mixed with 65 parts of deionized water, 9 parts of a mixture of sodium dodecyl sulfate and isomeric tridecanol ethoxylate, 0.7 parts of NaHCO with a mass concentration of 0.25%, and 1.5 parts of ethyl acetate. 3After the mixture is uniformly mixed with 1.8 parts of a 10% dibenzoyl peroxide solution, the mixture is stirred at 80°C at a stirring speed of 300 r / min for 2 hours, and then 4 parts of hexafluorobutyl acrylate monomer and 0.4 parts of a 10% dibenzoyl peroxide solution are slowly dripped into the mixed system under stirring within 3 hours, and the mixture is cooled to 30°C, and a 3% volume concentration of 2-amino-2-methyl-1-propanol solution is added to neutralize the pH to 7.6 to obtain a fluorine-containing acrylate emulsion; wherein the mass ratio of butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate and methacrylic acid is 1:1:1:1, and the mass ratio of sodium dodecyl sulfate to the volume ratio of isomeric tridecyl alcohol ethoxylate is 1:1.

[0048] Slowly add 10 parts of deionized water to 4 parts of riboflavin powder, and stir magnetically for 15 minutes to obtain a riboflavin suspension; slowly add 10 parts of deionized water to 20 parts of magnesium fluoride powder, and stir magnetically for 15 minutes to obtain a magnesium fluoride suspension; after mixing 30 parts of riboflavin suspension with 20 parts of magnesium fluoride suspension, add 1.2 parts of 3-aminopropyltriethoxysilane, stir for 15 minutes to mix, slowly add acetic acid solution with a mass concentration of 66.7% to the solution, adjust the pH value to 4.6, react at 45°C for 4.5 hours, and dry at 50°C for 3.5 hours to obtain a magnesium fluoride / riboflavin complex.

[0049] 5 parts of polyethylene glycol, 2 parts of castor oil, 10 parts of toluene diisocyanate and 30 parts of N,N-dimethylformamide were mixed evenly and heated and stirred at 65°C for 6.5 hours. 3.5 parts of citric acid were added and stirred for 3.5 hours, and then 4 parts of glucose were added and stirred for 4 hours to obtain a bio-based polyurethane oligomer.

[0050] 26 parts of fluorine-containing acrylic emulsion, 13 parts of bio-based polyurethane oligomer, 1.6 parts of magnesium fluoride / riboflavin complex, 0.7 parts of triethanolamine solution with a volume concentration of 20%, and 4.5 parts of resorcinol diglycidyl ether were uniformly mixed to prepare a photoresist composition.

[0051] Example 5

[0052] 17 parts of acrylic acid ester mixed monomers were mixed with 60 parts of deionized water, 11 parts of a mixture of sodium dodecyl sulfate and isomeric tridecanol ethoxylate, and 1 part of a 0.25% mass concentration of NaHCO 3After the mixture is uniformly mixed with 1.8 parts of a 10% dibenzoyl peroxide solution, the mixture is stirred at 80°C at a stirring speed of 300 r / min for 2-3 hours, and then 3 parts of hexafluorobutyl acrylate monomer and 0.5 parts of a 10% dibenzoyl peroxide solution are slowly dripped into the mixed system under stirring within 3 hours, and the mixture is cooled to 20°C, and a 3% volume concentration of 2-amino-2-methyl-1-propanol solution is added to neutralize the pH to 8.0 to obtain a fluorinated acrylate emulsion; wherein the mass ratio of butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate and methacrylic acid is 1:1:1:1, and the mass ratio of sodium dodecyl sulfate to the volume ratio of isomeric tridecyl alcohol ethoxylate is 1:1.

[0053] Slowly add 10 parts of deionized water to 4 parts of riboflavin powder, and stir magnetically for 15 minutes to obtain a riboflavin suspension; slowly add 10 parts of deionized water to 20 parts of magnesium fluoride powder, and stir magnetically for 15 minutes to obtain a magnesium fluoride suspension; after mixing 30 parts of riboflavin suspension with 20 parts of magnesium fluoride suspension, add 1.2 parts of 3-aminopropyltriethoxysilane, stir for 15 minutes to mix, slowly add 66.7% acetic acid solution dropwise to the solution, adjust the pH value to 4.0, react at 40°C for 4 hours, and dry at 50°C for 3 hours to obtain a magnesium fluoride / riboflavin complex.

[0054] 5 parts of polyethylene glycol, 2 parts of castor oil, 10 parts of toluene diisocyanate and 30 parts of N, N-dimethylformamide were mixed evenly and heated and stirred at 60°C for 6 hours. 4 parts of citric acid were added and stirred for 5 hours, and then 3 parts of glucose were added and stirred for 3 hours to obtain a bio-based polyurethane oligomer.

[0055] A photoresist composition was prepared by uniformly mixing 27 parts of fluorine-containing acrylic emulsion, 12 parts of bio-based polyurethane oligomer, 2 parts of magnesium fluoride / riboflavin complex, 1 part of triethanolamine solution with a volume concentration of 20%, and 4 parts of phenyl glycidyl ether.

[0056] The present invention also carries out comparative examples and related tests.

[0057] Comparative Example 1

[0058] The only difference compared with Example 1 is that the fluorinated acrylate emulsion is not prepared, but the acrylate emulsion is prepared directly from the acrylate mixed monomer, that is, 15 parts of the acrylate mixed monomer is mixed with 60 parts of deionized water, 8 parts of a mixture of sodium dodecyl sulfate and isomeric tridecanol ethoxylate, 0.7 parts of 0.25% NaHCO 3The solution and 1.5 parts of 10% dibenzoyl peroxide solution were mixed evenly, and the mixture was stirred at 80°C at a stirring speed of 300 r / min for 2.5 hours, then cooled to 25°C, and 3% volume concentration of 2-amino-2-methyl-1-propanol solution was added to neutralize the pH to 7.2 to obtain an acrylate emulsion. The other components and preparation steps were completely consistent to obtain a photoresist composition.

[0059] Comparative Example 2

[0060] The only difference compared with Example 1 is that citric acid is not added in the process of preparing the bio-based polyurethane oligomer, and the other components and preparation steps are completely the same to prepare a photoresist composition.

[0061] Comparative Example 3

[0062] The only difference compared with Example 1 is that the magnesium fluoride / riboflavin complex is not prepared, and riboflavin is directly added as a photoinitiator. The other components and preparation steps are completely the same to prepare a photoresist composition.

[0063] Performance testing

[0064] The photoresist compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were stirred evenly, coated, dried, and irradiated under ultraviolet light for 90 seconds to prepare photoresists. The prepared photoresists were tested for basic properties according to ASTM D-882. The test results are shown in Table 1.

[0065] Table 1

[0066]

[0067] As can be seen from Table 1, the basic performances of Examples 1 to 5 are significantly better than those of Comparative Examples 1 to 3, among which, the water absorption rate, alkali resistance and surface energy of the film of Comparative Example 1 in which the fluorine-containing acrylate emulsion is not prepared are worse than those of Example 1, and the water absorption rate, alkali resistance and surface energy of the photoresist composite film of Comparative Example 2 in which the bio-based polyurethane oligomer is not prepared are also significantly worse than those of Example 1; compared with Comparative Example 3, the basic performances of Example 1 with the addition of magnesium fluoride are significantly improved.

[0068] The photoresist composites prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were subjected to resolution and etching resistance tests. In the resolution test, the prepared photoresist composite was coated on a glass substrate coated with ITO and pre-baked at 90°C for 3 minutes, and a film was covered on the dried sample and pre-baked at 200 mJ / cm 2 UV exposure: the exposed glass sample is placed in a KOH aqueous solution with a mass concentration of 0.5% to develop and form a pattern; the etching resistance test: the photoresist spin-coated on the silicon wafer is plasma etched in an ammonia atmosphere for 15 seconds, and the relative loss of the photoresist film thickness is calculated.

[0069] Table 2

[0070]

[0071] It can be seen from Table 2 that the resolution and etching resistance of the photoresist composites prepared by the preparation methods of Examples 1 to 5 are significantly improved when used as photoresists.

[0072] The photoresist composites prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were subjected to an alkali etching durability test, and a wet etching experiment was performed within 0 to 25 seconds. The experimental steps are as follows: the photoresist samples prepared by the above basic performance test were respectively placed in a NaOH solution with a mass concentration of 1%, and were taken out after 5 seconds, 10 seconds, 15 seconds, 20 seconds, and 25 seconds, respectively, and the samples were rinsed with deionized water, and the thickness was measured after drying in an oven. The test results are shown in FIG. Figure 1 shown.

[0073] Depend on Figure 1 It can be seen that the thickness change of the photoresist samples prepared by using the photoresist composites prepared in Examples 1 to 5 in a NaOH solution with a mass concentration of 1% from 0 to 25 s is significantly smaller than that of Comparative Examples 1 to 3, and the alkali etching durability is significantly improved.

[0074] The above are preferred embodiments of the present invention. It should be pointed out that, for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a photoresist composition, characterized in that: The following steps are involved: S1. After uniformly mixing the acrylic ester mixed monomer, deionized water, a mixture of sodium dodecyl sulfate and isomeric tridecanol ethoxylates, a NaHCO3 solution, and a dibenzoyl peroxide solution, stirring for reaction, slowly dropping the hexafluorobutyl acrylate monomer and the dibenzoyl peroxide solution, and cooling to obtain a fluorinated acrylic ester emulsion; S2, mixing polyethylene glycol, toluene diisocyanate and N,N-dimethylformamide evenly, heating and stirring, adding citric acid and stirring to react, thereby obtaining a bio-based polyurethane oligomer; S3. Evenly mix the fluorine-containing acrylic emulsion, the bio-based polyurethane oligomer, the magnesium fluoride / riboflavin complex, and the active diluent to prepare a photoresist composition.

2. The method for preparing a photoresist composition according to claim 1, characterized in that: The acrylic ester mixed monomer in step S1 is a mixture of butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate and methacrylic acid, wherein the mass ratio of butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate and methacrylic acid is 1:1:1:1; the mass ratio of the sodium dodecyl sulfate to the volume ratio of the isomeric tridecanol ethoxylate is 1:1, the mass concentration of the NaHCO3 solution is 0.25%, and the mass concentration of the dibenzoyl peroxide solution is 10%.

3. The method for preparing a photoresist composition according to claim 1, characterized in that: In the step S1, the reaction is stirred at 75-80° C. at a stirring speed of 300 r / min for 2-3 hours, the hexafluorobutyl acrylate monomer and the dibenzoyl peroxide solution are slowly dripped into the mixed system under stirring within 3 hours, and the mixture is cooled to 20-35° C., and a 2-amino-2-methyl-1-propanol solution with a volume concentration of 3% is added to neutralize the pH to 7.0-8.0 to obtain a fluorinated acrylate emulsion.

4. The method for preparing a photoresist composition according to claim 1, characterized in that: In the step S2, castor oil is added, polyethylene glycol, toluene diisocyanate and N,N-dimethylformamide are mixed evenly, and heated and stirred at 55-65° C. for 5-7 hours.

5. The method for preparing a photoresist composition according to claim 1, characterized in that: In the step S2, citric acid is added and stirred for reaction for 3 to 5 hours, and then glucose is added and stirred for reaction for 2 to 4 hours, so as to finally obtain a bio-based polyurethane oligomer.

6. The method for preparing a photoresist composition according to claim 1, characterized in that: In step S3, the magnesium fluoride / riboflavin complex is prepared by mixing a riboflavin suspension and a magnesium fluoride suspension, adding 3-aminopropyltriethoxysilane, stirring and mixing, adding an acetic acid solution to adjust the pH value to 4.0-5.0, reacting at 40-50° C. for 4-6 hours, and drying at 50° C. for 2-4 hours.

7. The method for preparing a photoresist composition according to claim 6, characterized in that: The mass concentration of the acetic acid solution is 66.7%; the riboflavin suspension is obtained by slowly adding deionized water to riboflavin powder and magnetically stirring for 15 minutes; the magnesium fluoride suspension is obtained by slowly adding deionized water to magnesium fluoride powder and magnetically stirring for 15 minutes.

8. The method for preparing a photoresist composition according to claim 1, characterized in that: In the step S3, triethanolamine solution is further added and mixed evenly with fluorinated acrylic emulsion, bio-based polyurethane oligomer, magnesium fluoride / riboflavin complex and active diluent; wherein the active diluent is one of phenyl glycidyl ether, diepoxy ethylene glycol diglycidyl ether and resorcinol diglycidyl ether, and the volume concentration of the triethanolamine solution is 20%.

9. A photoresist composition, characterized in that: The photoresist composition is prepared by the preparation method of any one of claims 1 to 8, comprising the following raw materials in parts by weight: 20 to 30 parts of fluorine-containing acrylate emulsion, 10 to 15 parts of bio-based polyurethane oligomer, 1 to 2 parts of magnesium fluoride / riboflavin complex, 0.5 to 1 part of triethanolamine solution, and 3 to 6 parts of active diluent.

10. A photoresist composition according to claim 9, characterized in that: The raw materials of the fluorine-containing acrylic emulsion include 10-20 parts of acrylic ester mixed monomers, 50-70 parts of deionized water, 6-12 parts of a mixture of sodium dodecyl sulfate and isomeric tridecanol ethoxylates, 0.5-1 parts of NaHCO3 solution, and 1.3-2.5 parts of dibenzoyl peroxide solution, calculated by weight; the raw materials of the magnesium fluoride / riboflavin complex include 30 parts of riboflavin suspension, 20 parts of magnesium fluoride suspension, and 1.2 parts of 3-aminopropyltriethoxysilane, calculated by volume; the raw materials of the bio-based polyurethane include 5 parts of polyethylene glycol, 2 parts of castor oil, 10 parts of toluene diisocyanate, 30 parts of N,N-dimethylformamide, 3-5 parts of citric acid, and 2-5 parts of glucose, calculated by weight.

Images