Silicon-free defoaming agent and preparation of developing solution thereof

Abstract

The invention discloses a silicon-free defoaming agent and a preparation method of a developing solution thereof, and relates to the technical field of developing solutions. In a carbonization reaction system for preparing calcium carbonate, a hydrophobic modifier and gallic acid are grafted to the surfaces of particles through chemical bonds, in developing liquid, adjacent bubbles are connected through particle physical interception and Van der Waals force, meanwhile, the bridging-dehumidification speed is increased through the hydrophobic function, the defoaming effect is achieved, and the defoaming effect is achieved. Gallic acid is combined with nano-particles to form an amphiphilic interface, the defoaming efficiency is further improved, so that the developing effect is enhanced, then gallic acid on the surfaces of the nano-particles is subjected to esterification treatment, the developing effect of a matrix is further enhanced, finally, in a developing solution system, gallic acid is combined with nano-crystalline cellulose, the uniformity of liquid is maintained, and the developing precision is improved; and through the synergistic effect of the cellulose and the particles, the defoaming and developing effects are enhanced.

Description

Technical Field

[0001] The present invention relates to the technical field of developer solutions, in particular to a silicon-free defoaming agent and preparation of a developer solution thereof. Background Art

[0002] Photoresist is widely used in forming wiring patterns for integrated circuits, printed circuit boards, color liquid crystal displays, and color filters. During the wiring pattern formation process, a pigment dispersion, solvent, photosensitive resin, and related additives are first mixed to form a photoresist. The photoresist is then coated onto a substrate and pre-baked. After exposure with a photomask, the unexposed portions of the photoresist are washed away with a developer to produce the desired photoresist pattern. However, when developing the photoresist, air enters the developer, causing foaming. If this foam is not adequately defoamed, it accumulates in the developer. As the amount of photoresist dissolved or dispersed in the developer increases, the foam in the developer becomes difficult to eliminate. This foam hinders contact between the developer and the photoresist, resulting in inadequate removal of the unexposed portions and poor formation of a good photoresist pattern. Furthermore, the currently predominant jet development method, which involves spraying the developer onto the exposed photoresist, is more susceptible to foaming in the developer.

[0003] In traditional processes, silicone defoamers are commonly used to eliminate foam generated during development and film stripping. While silicone defoamers offer good defoaming effects, the poor water solubility of the inorganic silicon in these defoamers and their reaction with the dry film can cause sticky substances to adhere to the copper surface, leading to reduced board quality and manufacturing capacity. This is especially true given the increasing sophistication of electronic products. Furthermore, silicone defoamers can demulsify under specific conditions, such as high temperatures, strong acids, and strong bases, resulting in poor defoaming performance. Consequently, a growing number of industries are prohibiting the use of silicone defoamers. Therefore, the development of a silicone-free defoamer for use in developer solutions is particularly necessary. Summary of the Invention

[0004] The purpose of the present invention is to provide a silicon-free defoaming agent and a developer thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solution: a silicon-free defoaming agent, comprising the following preparation steps:

[0006] (1) Dissolve calcium oxide in deionized water at 80°C, then pass through a 200-mesh sieve, blend with the modifier, stir at 800 rpm for 40-70 minutes, and then 3 / min, and the mixed gas was introduced to react until the pH of the solution reached 7. Finally, it was washed with deionized water 5 times and dried at 60 ° C for 8 h to obtain intermediate A;

[0007] (2) Intermediate A, cyclohexane, propanol, and catalyst are mixed, and then the temperature is raised to 80-120°C, reacted for 10-20 hours, and washed with deionized water 5 times to obtain a silicon-free defoaming agent.

[0008] Furthermore, the mixed gas in step (1) is carbon dioxide and nitrogen, and the volume ratio of the two is 3:7-12.

[0009] Furthermore, the mass ratio of calcium oxide, deionized water and modifier in step (1) is 10:100:100.

[0010] Furthermore, the modifier in step (1) is composed of gallic acid, sodium stearate, octadecanol phosphate, oleic acid, and ethanol, and the mass ratio thereof is 1:0.5 to 1:0.3:0.1:300.

[0011] Furthermore, in step (2), the mass ratio of the intermediate A, cyclohexane, propanol, and catalyst is 1:100:3:0.01-0.1.

[0012] A method for preparing a developer, characterized in that it comprises the following preparation steps:

[0013] Diglycolamine was dissolved in deionized water, heated to 60°C, stirred at 100 rpm for 10 min, nanocellulose and silicon-free defoaming agent were added in sequence, ultrasonicated at 40 kHz for 30 min, the pH of the solution was adjusted to 9.5 with disodium hydrogen phosphate, and a chelating agent, a wetting agent, and a solvent were added to obtain a developer.

[0014] Furthermore, the mass ratio of the diglycolamine, deionized water, nanocellulose, silicon-free defoaming agent, chelating agent, wetting agent and solvent is 2-4:30:1:1-3:0.05:0.1-0.3:60.

[0015] Furthermore, the nanocellulose has a diameter of 5 to 30 nm and a length of 100 to 200 nm.

[0016] Furthermore, the solvent consists of deionized water, ethanol, and PEG400 in a mass ratio of 6:0.3:0.1.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] The present invention uses nano calcium carbonate and gallic acid as raw materials to prepare a defoaming agent. In the carbonization reaction system for preparing calcium carbonate, a hydrophobic modifier and gallic acid are grafted onto the particle surface through chemical bonds. In the developing liquid, the particles are first physically trapped and particle bridges are formed between bubbles. Adjacent bubbles are connected by van der Waals forces, promoting bubble aggregation and rupture. At the same time, the hydrophobic function accelerates the speed of "bridging-dehumidification" and further reduces the thickness of the liquid film, thereby achieving a defoaming effect. The combination of gallic acid and nanoparticles can enhance the adsorption capacity of gallic acid and adsorb the developer. Extremely tiny bubbles form an amphiphilic interface through the hydrophobic groups on the surface of the particles and the hydrophilic hydroxyl groups of gallic acid, further improving the defoaming efficiency, thereby reducing photoresist residue and enhancing the development effect. The gallic acid on the surface of the nanoparticles is then esterified to improve the antioxidant properties of the matrix, thereby enhancing the development effect of the developer. Finally, in the developer system, it combines with nanocellulose and adsorbs the developing particles through hydrogen bonds and electrostatic effects, maintaining the uniformity of the liquid and improving the development accuracy. The cellulose enhances the defoaming and development effects through the synergistic effect with the particles. DETAILED DESCRIPTION

[0019] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0020] In order to more clearly illustrate the method provided by the present invention, the following examples are provided in detail. The test methods for various indicators of the developer prepared in the following examples are as follows:

[0021] Development: Take the example and comparative example of the same size and dilute them 100 times. After developing at 23°C for 80 seconds, take out the above test piece, rinse it in ultrapure water, dry it with nitrogen, and then bake it at 230°C for 20 minutes. Observe the above developed test piece with an electron microscope to evaluate whether the non-exposed part around the formed pattern remains and the pattern edge of the photoresist.

[0022] Example 1

[0023] (1) Calcium oxide was dissolved in deionized water at 80°C, then passed through a 200-mesh sieve, mixed with the modifier, stirred at 800 rpm for 40 min, and then sieved at 1 dm 3 / min, and react until the solution pH reaches 7, and finally wash with deionized water 5 times, and dry at 60 ° C for 8 h to obtain intermediate A; the mixed gas is carbon dioxide and nitrogen, and the volume ratio of the two is 3:7; the mass ratio of the calcium oxide, deionized water, and the modifier is 10:100:100; the modifier is composed of gallic acid, sodium stearate, octadecanol phosphate, oleic acid, and ethanol, and the mass ratio is 1:0.5:0.3:0.1:300;

[0024] (2) Intermediate A, cyclohexane, propanol, and a catalyst were mixed, and then heated to 80° C., reacted for 10 hours, and washed 5 times with deionized water to obtain a silicon-free defoamer; the mass ratio of the intermediate A, cyclohexane, propanol, and acid catalyst was 1:100:3:0.01; the catalyst was [PIL-SO3][PhA];

[0025] (3) Dissolve diglycolamine in deionized water, heat to 60°C, stir at 100 rpm for 10 min, add nanocellulose and silicon-free defoaming agent in sequence, ultrasonicate at 40 kHz for 30 min, adjust the pH of the solution to 9.5 with disodium hydrogen phosphate, add a chelating agent, a wetting agent, and a solvent to obtain a developer; the mass ratio of the diglycolamine, deionized water, nanocellulose, silicon-free defoaming agent, chelating agent, wetting agent, and solvent is 2:30:1:1:0.05:0.1:60; the diameter of the nanocellulose is 5 nm and the length is 100 nm; the solvent consists of deionized water, ethanol, and PEG400 in a mass ratio of 6:0.3:0.1; the chelating agent is disodium ethylenediaminetetraacetic acid; and the wetting agent is sodium dodecylbenzenesulfonate.

[0026] Example 2

[0027] (1) Calcium oxide was dissolved in deionized water at 80°C, then passed through a 200-mesh sieve, mixed with the modifier, stirred at 800 rpm for 50 min, and then sieved with 1 dm 3 / min, and react until the solution pH reaches 7, and finally wash with deionized water 5 times, and dry at 60 ° C for 8 h to obtain intermediate A; the mixed gas is carbon dioxide and nitrogen, and the volume ratio of the two is 3:5; the mass ratio of the calcium oxide, deionized water, and the modifier is 10:100:100; the modifier is composed of gallic acid, sodium stearate, octadecanol phosphate, oleic acid, and ethanol, and the mass ratio is 1:0.8:0.3:0.1:300;

[0028] (2) Intermediate A, cyclohexane, propanol, and a catalyst were mixed, and then heated to 100° C., reacted for 15 hours, and washed 5 times with deionized water to obtain a silicon-free defoamer; the mass ratio of intermediate A, cyclohexane, propanol, and acid catalyst was 1:100:3:0.06; the catalyst was [PIL-SO3][PhA];

[0029] (3) Dissolve diglycolamine in deionized water, heat to 60°C, stir at 100 rpm for 10 min, add nanocellulose and silicon-free defoaming agent in sequence, ultrasonicate at 40 kHz for 30 min, adjust the pH of the solution to 9.5 with disodium hydrogen phosphate, add a chelating agent, a wetting agent, and a solvent to obtain a developer; the mass ratio of the diglycolamine, deionized water, nanocellulose, silicon-free defoaming agent, chelating agent, wetting agent, and solvent is 3:30:1:2:0.05:0.2:60; the diameter of the nanocellulose is 18 nm and the length is 150 nm; the solvent consists of deionized water, ethanol, and PEG400 in a mass ratio of 6:0.3:0.1; the chelating agent is disodium ethylenediaminetetraacetic acid; and the wetting agent is sodium dodecylbenzenesulfonate.

[0030] Example 3

[0031] (1) Calcium oxide was dissolved in deionized water at 80°C, then passed through a 200-mesh sieve, mixed with the modifier, stirred at 800 rpm for 70 min, and then sieved at 1 dm 3 / min, and react until the solution pH reaches 7, and finally wash with deionized water 5 times, and dry at 60°C for 8h to obtain intermediate A; the mixed gas is carbon dioxide and nitrogen, and the volume ratio of the two is 3:12; the mass ratio of the calcium oxide, deionized water, and modifier is 10:100:100; the modifier is composed of gallic acid, sodium stearate, octadecanol phosphate, oleic acid, and ethanol, and the mass ratio is 1:1:0.3:0.1:300;

[0032] (2) Intermediate A, cyclohexane, propanol, and a catalyst were mixed, and then heated to 120° C., reacted for 20 hours, and washed 5 times with deionized water to obtain a silicon-free defoamer; the mass ratio of the intermediate A, cyclohexane, propanol, and acid catalyst was 1:100:3:0.1; the catalyst was [PIL-SO3][PhA];

[0033] (3) Dissolve diglycolamine in deionized water, heat to 60°C, stir at 100 rpm for 10 min, add nanocellulose and silicon-free defoaming agent in sequence, ultrasonicate at 40 kHz for 30 min, adjust the pH of the solution to 9.5 with disodium hydrogen phosphate, add a chelating agent, a wetting agent, and a solvent to obtain a developer; the mass ratio of diglycolamine, deionized water, nanocellulose, silicon-free defoaming agent, chelating agent, wetting agent, and solvent is 4:30:1:3:0.05:0.3:60; the diameter of the nanocellulose is 30 nm and the length is 200 nm; the solvent consists of deionized water, ethanol, and PEG400 in a mass ratio of 6:0.3:0.1; the chelating agent is disodium ethylenediaminetetraacetic acid; and the wetting agent is sodium dodecylbenzenesulfonate.

[0034] Comparative Example 1

[0035] The difference between Comparative Example 1 and Example 2 is that step (1) is omitted, and step (2) is changed to: gallic acid, cyclohexane, propanol, and a catalyst are mixed, and then the temperature is raised to 100° C., reacted for 15 hours, and washed 5 times with deionized water to obtain a silicon-free defoamer; the mass ratio of the gallic acid, cyclohexane, propanol, and acid catalyst is 1:100:3:0.06; the catalyst is [PIL-SO3][PhA]; and the remaining steps are the same as in Example 2.

[0036] Comparative Example 2

[0037] The difference between Comparative Example 2 and Example 2 is that step (1) is different. Step (1) is changed to: calcium oxide is dissolved in deionized water at 80°C, then passed through a 200-mesh sieve, blended with the modifier, stirred at 800 rpm for 50 min, and then sieved at 1 dm 3 / min, and react until the pH of the solution reaches 7. Finally, the mixture is washed with deionized water 5 times and dried at 60°C for 8 h to obtain intermediate A; the mixed gas is carbon dioxide and nitrogen, and the volume ratio of the two is 3:5; the mass ratio of the calcium oxide, deionized water, and the modifier is 10:100:100; the modifier is composed of sodium stearate, octadecanol phosphate, oleic acid, and ethanol, and the mass ratio is 0.8:0.3:0.1:300; the remaining steps are the same as in Example 2.

[0038] Comparative Example 3

[0039] The difference between Comparative Example 3 and Example 2 is that there is no step (2); the remaining steps are the same as Example 2.

[0040] Comparative Example 4

[0041] The difference between Comparative Example 4 and Example 2 is that step (3) is different. Step (3) is changed to: dissolve diglycolamine in deionized water, heat to 60°C, stir at 100 rpm for 10 min, add silicon-free defoamer in sequence, ultrasonicate at 40 kHz for 30 min, adjust the pH of the solution to 9.5 with disodium hydrogen phosphate, add a chelating agent, a wetting agent, and a solvent to obtain a developer; the mass ratio of the diglycolamine, deionized water, silicon-free defoamer, chelating agent, wetting agent, and solvent is 3:30:2:0.05:0.2:60; the solvent is composed of deionized water, ethanol, and PEG400 in a mass ratio of 6:0.3:0.1; the chelating agent is disodium ethylenediaminetetraacetic acid; the wetting agent is sodium dodecylbenzenesulfonate; and the remaining steps are the same as in Example 2.

[0042] Effect Examples

[0043] Table 1 below shows the performance analysis results of the developers of Examples 1 to 3 and Comparative Examples 1 to 4 of the present invention.

[0044] Table 1

[0045] Developing effect Example 1 Very good Example 2 Very good Example 3 Very good Comparative Example 1 Poor Comparative Example 2 Poor Comparative Example 3 Good Comparative Example 4 Poor

[0046] From the comparison of the experimental results of the embodiment and the comparative example in Table 1, it can be found that in the carbonization reaction system for preparing calcium carbonate of the present invention, a hydrophobic modifier is grafted to the particle surface through a chemical bond with gallic acid. In the developing liquid, the defoaming effect is achieved through the synergistic effect of physical retention of the particles and van der Waals force. Gallic acid is combined with nanoparticles to enhance the adsorption capacity of gallic acid and adsorb extremely small bubbles in the developer. The hydrophobic groups on the surface of the particles cooperate with the hydrophilic hydroxyl groups of gallic acid to form an amphiphilic interface, further improving the defoaming efficiency, thereby reducing photoresist residue and enhancing the developing effect. The gallic acid on the surface of the nanoparticles is then esterified to enhance the antioxidant property of the matrix, thereby enhancing the developing effect of the developer. Finally, in the developer system, it is combined with nanocellulose to adsorb the developing particles through hydrogen bonds and electrostatic effects, thereby improving the developing accuracy. The cellulose enhances the defoaming effect through the synergistic effect with the particles, thereby further improving the developing effect.

[0047] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A silicon-free defoamer, characterized in that: The method comprises the following preparation steps: (1) Calcium oxide is dissolved in deionized water at 80°C, then sieved, mixed with a modifier, and vigorously stirred for 40 to 70 minutes. Then, a mixed gas is introduced and reacted until the solution pH reaches 7. Finally, the solution is washed and dried to obtain intermediate A. (2) Intermediate A, cyclohexane, propanol, and an acid catalyst are mixed, reacted, and washed to obtain a silicon-free defoaming agent.

2. A silicon-free defoamer according to claim 1, characterized in that, The mixed gas in step (1) is carbon dioxide and nitrogen, and the volume ratio of the two is 3:7-12.

3. A silicon-free defoamer according to claim 1, characterized in that, The mass ratio of calcium oxide, deionized water and modifier in step (1) is 10:100:

100.

4. A silicon-free defoamer according to claim 1, characterized in that, The modifier in step (1) is composed of gallic acid, sodium stearate, octadecanol phosphate, oleic acid, and ethanol, and the mass ratio thereof is 1:0.5 to 1:0.3:0.1:

300.

5. The silicon-free defoamer according to claim 1, characterized in that: The mass ratio of the intermediate A, cyclohexane, propanol and acid catalyst in step (2) is 1:100:3:0.01-0.

1.

6. A method for preparing a developer, characterized in that: The method comprises the following preparation steps: Dissolve diglycolamine in deionized water, add nanocellulose and silicon-free defoaming agent in sequence, adjust the pH value of the solution to 9.5 with disodium hydrogen phosphate, add a chelating agent, a wetting agent and a solvent to obtain a developer.

7. The method for preparing a developer according to claim 6, wherein: The mass ratio of the diglycolamine, deionized water, nanocellulose, silicon-free defoaming agent, chelating agent, wetting agent and solvent is 2-4:30:1:1-3:0.05:0.1-0.3:

60.

8. The method for preparing a developer according to claim 6, wherein: The silicon-free defoaming agent is the silicon-free defoaming agent according to claims 1 to 6.

9. The method for preparing a developer according to claim 6, wherein: The nanocellulose has a diameter of 5 to 30 nm and a length of 100 to 200 nm.

10. The method for preparing a developer according to claim 6, wherein: The solvent consists of deionized water, ethanol and PEG400, and the mass ratio thereof is 6:0.3:0.1.