A quadruple structure emulsifier for developer and a preparation method thereof

Abstract

The application discloses a tetrad structure emulsifier for developing solution and a preparation method thereof. The emulsifier is a novel emulsifier containing four hydrophilic head groups and four hydrophobic tail chains in a single molecule, which is prepared by the following steps: reacting 2,2-bishydroxymethyl-1,3-propanediol and phosphorus oxychloride in the presence of an acid binding agent and tetrahydrofuran, continuously reacting by dropwise adding a long-chain fatty alcohol, and treating by hydrolysis dechlorination and sodium ethoxide ethanol solution. The tetrad structure emulsifier prepared by the application has a smaller spacing between the hydrophilic head groups than common surfactants due to the strong force of covalent bond, so that the critical micelle concentration is lower, the emulsifying performance is better, and the performance in the application of the developing solution is better.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of surfactant preparation, and particularly relates to a tetrad structure emulsifier for a developing solution and a preparation method thereof. BACKGROUND

[0002] In the field of flat panel display, especially in large-size display devices, TFT-LCD technology is the current mainstream process. In the photolithography process of TFT-LCD color filter manufacturing, in order to obtain various fine images required, a photoresist is coated on a substrate to form a thin film, and then a specific pattern mask is used to shield and expose light, so that the developing solution is developed, and the soluble resin part not exposed to light is removed, so as to obtain the required image. The CF process is divided into multiple processes such as black matrix layer (BM), color resist layer (R, G, B), gap column layer (PS) and protective layer (OC). Each process has a complete photolithography process: cleaning, glue coating, soft baking, exposure, development, hard baking, and then accurate patterns are obtained through detection to proceed to the next step. Therefore, it is crucial for the yield of products to improve the developing speed, the clearness and accuracy of patterns, the stability of CD value, and to meet the low-foaming performance of high-pressure spraying and the non-residual easy-developing performance of the developing solution in the process.

[0003] The mainstream developing solution for CF process on the market at present is mainly an alkaline developing solution, which mainly includes alkaline substances, surfactants and high-purity water. However, with the popularization of 4k images on the market and the development of 8k images in the future, the developing precision is required to be higher in the technical process, and a precise image needs to be formed after development. In order to improve the poor developing performance caused by the residual particles or undissolved substances in the un-developed part, a more efficient developing solution is required to meet the process requirements. The surfactant added in the developing solution at present is mainly a single-chain surfactant, which has limited performance due to the influence of intermolecular repulsion, and has poor alkali resistance and temperature resistance. In order to obtain a more efficient developing solution, a surfactant with more excellent performance needs to be prepared and applied in the formula of the developing solution. SUMMARY

[0004] In order to enrich the types of surfactants specially used in the field of developing solution manufacturing, the application provides a tetrad structure emulsifier and a preparation method thereof.

[0005] To achieve the above-mentioned purpose, the application adopts the following technical solutions:

[0006] A tetrad structure emulsifier for a developing solution has the following chemical structure formula:

[0007] , wherein: R = C 10 H 21 or C 12 H 25 .

[0008] The synthesis reaction formula of the tetrad structure emulsifier is as follows: ; the preparation method comprises the following steps:

[0009] (1) a certain amount of 2,2-bishydroxymethyl-1,3-propanediol and phosphorus oxychloride are added into a reactor provided with an acid-binding agent and tetrahydrofuran, and the reactor is kept at 60 DEG C for reflux reaction for 4 hours, then a certain amount of long-chain fatty alcohol is added dropwise under stirring condition, and the reaction is continued for 6 hours, and then the intermediate product I is obtained after purification by recrystallization;

[0010] (2) the intermediate product I prepared in step (1) is hydrolyzed and dechlorinated, and then stirred with a certain amount of sodium ethoxide ethanol solution at 80 DEG C for 6 hours; after centrifugal separation, the supernatant is discarded, the obtained solid layer is washed with anhydrous ethanol for 3 times, and then the tetrad structure emulsifier is prepared after vacuum drying.

[0011] Further, the acid-binding agent in step (1) is pyridine or triethylamine, and the molar ratio of 2,2-bishydroxymethyl-1,3-propanediol to the acid-binding agent is 1: (12-16).

[0012] Further, the molar ratio of 2,2-bishydroxymethyl-1,3-propanediol to phosphorus oxychloride used in step (1) is 1: (4.2-4.4).

[0013] Further, the long-chain fatty alcohol in step (1) is C 10 H 21 OH or C 12 H 25 OH, and the molar ratio of 2,2-bishydroxymethyl-1,3-propanediol to the long-chain fatty alcohol is 1: (4.2-4.4).

[0014] Further, the hydrolysis and dechlorination in step (2) is carried out by immersing the intermediate product I in a high-pressure kettle at 220 DEG C for 2 hours using a 4% NaOH aqueous solution.

[0015] Further, the mass ratio of the sodium ethoxide ethanol solution to the intermediate product I used in step (2) is 4:1, wherein the mass concentration of the sodium ethoxide ethanol solution is 95%.

[0016] Further, the centrifugal speed in step (2) is 8000-10000 r / min, and the time is 5 minutes.

[0017] The prepared tetrad structure emulsifier can be used for preparing a CF process developing solution.

[0018] Compared with the prior art, the present application has the following advantages and beneficial effects:

[0019] (1) The emulsifier prepared by the present application is a tetrad structure, which contains four hydrophilic head groups and four hydrophobic tail chains, and the spacing of the hydrophilic head groups is smaller by using the strong force of covalent bond, thereby the critical micelle concentration of the emulsifier is lower;

[0020] (2) The emulsifier prepared by the present application has good alkali resistance, can resist 15% NaOH solution without precipitation, and thus can be applied to the preparation of high-concentration developing solution, effectively reducing the production and transportation cost of the developing solution;

[0021] (3) The emulsifier prepared by the present application has stronger performance, better emulsification of oil and soluble resin, and can maintain the stable state of the developing solution. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 The surface tension test result graph of the tetrad structure emulsifier disclosed by the present application.

[0023] Figure 2 The H-NMR graph of the tetrad structure emulsifier prepared in Example 1. 1 H-NMR graph.

[0024] Figure 3 The H-NMR graph of the tetrad structure emulsifier prepared in Example 2. 1 H-NMR graph. DETAILED DESCRIPTION

[0025] In order to make the content of the present application more convenient to understand, the technical solutions of the present application will be further described below in combination with specific embodiments, but the present application is not limited thereto.

[0026] Example 1

[0027] 1) In a three-necked flask equipped with a reflux condenser, a dropping funnel and a stirrer, 12.12 g (0.12 mol) of triethylamine and 30 ml of tetrahydrofuran were added, then 1.36 g (0.01 mol) of 2,2-bishydroxymethyl-1,3-propanediol and 6.43 g (0.042 mol) of phosphorus oxychloride were sequentially added, the temperature was raised to 60℃ and refluxed and stirred for 4 h, after the reaction was completed, the reaction condition was maintained, 6.64 g (0.042 mol) of n-decanol was added, and the stirring reaction was continued for 6 h, after the reaction was completed, the intermediate product I was obtained by recrystallization with diethyl ether;

[0028] 2) In a high-pressure reactor, 10.91 g (0.01 mol) of intermediate product I was added, followed by 100 g of 4% NaOH aqueous solution, heated to 220°C for 2 h, and the product obtained after the reaction was stirred at 80°C for 6 h with 45 g of 95% sodium ethoxide ethanol solution. The product was centrifuged at a speed of 10000 r / min after the reaction was completed, the supernatant was discarded, the solid layer was washed with anhydrous ethanol for 3 times and vacuum dried to obtain the emulsifier with tetrad structure.

[0029] Example 2

[0030] 1) In a three-necked flask equipped with a reflux condenser, a dropping funnel and a stirrer, 9.48 g (0.12 mol) of pyridine and 30 ml of tetrahydrofuran were added, followed by 1.36 g (0.01 mol) of 2,2-bishydroxymethyl-1,3-propanediol and 6.73 g (0.044 mol) of phosphorus oxychloride, which was stirred at 60°C for 4 h. After the reaction was completed, 7.81 g (0.042 mol) of dodecanol was added, and the reaction was continued for 6 h. The intermediate product I was obtained by recrystallization with diethyl ether.

[0031] 2) In a high-pressure reactor, 13.39 g (0.01 mol) of intermediate product I was added, followed by 100 g of 4% NaOH aqueous solution, heated to 220°C for 2 h, and the product obtained after the reaction was stirred at 80°C for 6 h with 45 g of 95% sodium ethoxide ethanol solution. The product was centrifuged at a speed of 8000 r / min after the reaction was completed, the supernatant was discarded, the solid layer was washed with anhydrous ethanol for 3 times and vacuum dried to obtain the emulsifier with tetrad structure.

[0032] Example 3

[0033] 1) In a three-necked flask equipped with a reflux condenser, a dropping funnel and a stirrer, 16.16 g (0.16 mol) of triethylamine and 30 ml of tetrahydrofuran were added, followed by 1.36 g (0.01 mol) of 2,2-bishydroxymethyl-1,3-propanediol and 6.73 g (0.044 mol) of phosphorus oxychloride, which was stirred at 60°C for 4 h. After the reaction was completed, 8.18 g (0.044 mol) of dodecanol was added, and the reaction was continued for 6 h. The intermediate product I was obtained by recrystallization with diethyl ether.

[0034] 2) 13.39 g (0.01 mol) of intermediate product I was added to a high-pressure reactor, followed by 100 g of 4% NaOH aqueous solution. The mixture was heated to 220℃ and reacted for 2 h. After the reaction was completed, the product was stirred and refluxed at 80℃ with 45 g of 95% sodium ethoxide ethanol solution for 6 h. After the reaction was completed, the product was centrifuged at 8000 r / min, the supernatant was discarded, and the resulting solid layer was washed three times with anhydrous ethanol and dried under vacuum to obtain a tetrad emulsifier.

[0035] Surface tension test:

[0036] At room temperature, the two emulsifiers prepared in Examples 1 and 2 were respectively formulated into aqueous solutions of different concentrations, and then tested using the platinum plate method. The CMC concentration data of the emulsifiers were obtained from the test data, and the results are shown in [Figure 1]. Figure 1 .according to Figure 1 It can be seen that the two emulsifiers have slightly different properties due to the different hydrophobic chain lengths, but both maintain a low CMC concentration and can reduce the surface tension of water to below 30 mN / m when the CMC concentration is reached, which proves that the two emulsifiers have excellent surface activity.

[0037] Emulsification performance test:

[0038] At room temperature, 10 g of vegetable oil, 89 g of water, and 1 g of emulsifier were added to a beaker and stirred until homogeneous to obtain an emulsion. The emulsion was then quickly transferred to a graduated centrifuge tube and centrifuged at 4000 r / min for 15 min. The volume of the emulsion phase was then read, and the results were calculated using the following formula. The results are shown in Table 1.

[0039] .

[0040] Table 1. Emulsification test results of the four-component emulsifier.

[0041]

[0042] Application Examples:

[0043] In a 100 kg stirred tank, 70 kg of deionized water was added, stirring was started, 15 kg of potassium hydroxide was slowly added, stirring for 30 min to make it completely dissolved, then 10 kg of the tetrad structure emulsifier prepared in the example was added, stirring for 15 min, finally 5 kg of fatty alcohol polyoxyethylene-polyoxypropylene ether was added, stirring for 20 min, to obtain the developer. The stirring rate of the stirred tank was 30 rpm, and the stirring temperature was controlled below 50℃. At the same time, the developers prepared without adding emulsifier and using 2,2-bishydroxymethyl-1,3-propanediol or sodium dodecylbenzenesulfonate as the emulsifier were used as controls. The state of the obtained developer is shown in Table 1.

[0044] Table 1

[0045]

[0046] Performance test:

[0047] In order to verify the performance of the above developer, the following experimental scheme was used for determination.

[0048] 1. Preparation of glass substrate

[0049] Prepare the glass substrate sample, clean the glass substrate with special detergent, rinse with ultrapure water, and dry with nitrogen. A layer of 1.0 μm thick BM negative photoresist or R, G, B photoresist was spin-coated on each glass substrate by a spin coater, most of the solvent was extracted after vacuum extraction, and then pre-baking was carried out at 110℃ in an oven for 100 s, then the pattern on the mask was transferred to the glass substrate by exposure.

[0050] 2. Development test

[0051] The prepared developer was diluted 20-40 times with ultrapure water, the temperature of the liquid was controlled at 23℃, the diluted developer was sprayed on the glass substrate coated with photoresist at a constant pressure, the spraying time was 50 s, then ultrapure water was used for water washing, and nitrogen was used for drying. Optical microscope and electron microscope were used for observation to confirm whether the developed pattern was clear, whether the photoresist was left, whether the pattern edge was complete, whether there was a phenomenon of burr, how many pieces of glass substrate would cause obvious photoresist residue, and the service life of the developer. The results are shown in Table 2.

[0052] Table 2

[0053]

[0054] As can be seen from the results in Table 2, the developer prepared in the example is clear and transparent, stable in nature, and not easy to precipitate, which can achieve the advantages of suitable developing speed, clear pattern, complete edge, no photoresist residue, and long service life.

[0055] The above description is only the preferred embodiment of the present application, and any equivalent change and modification made according to the scope of the present application should be included in the scope of the present application.

Claims

1. A tetrad emulsifier for a developer, characterized by: The chemical structural formula is as follows: wherein: R = C 10 H 21 or C 12 H 25 .

2. A process for the preparation of a quadruple-structured emulsifier for a developer according to claim 1, characterized by: The method comprises the following steps: (1) a certain amount of 2,2-bishydroxymethyl-1,3-propanediol and phosphorus oxychloride are added into a reactor provided with an acid-binding agent and tetrahydrofuran, and the reactor is kept at 60 DEG C to reflux for 4 hours, then a certain amount of long-chain fatty alcohol is added dropwise under stirring, and the reaction is continued for 6 hours, and then the intermediate product I is obtained after recrystallization; (2) the intermediate product I obtained in step (1) is hydrolyzed and dechlorinated, and then is stirred with a certain amount of sodium ethoxide ethanol solution at 80 DEG C for 6 hours; after centrifugal separation, the supernatant is discarded, the obtained solid layer is washed with anhydrous ethanol for 3 times, and then is dried in vacuum to obtain the emulsifier with tetradentate structure; The molar ratio of 2,2-bishydroxymethyl-1,3-propanediol to phosphorus oxychloride used in step (1) is 1:(4.2-4.4); the long chain fatty alcohol is C 10 H 21 OH or C 12 H 25 OH, and the molar ratio of 2,2-bishydroxymethyl-1,3-propanediol to long chain fatty alcohol used is 1:(4.2-4.4).

3. A process for the preparation of a quadruple structured emulsifier for developer according to claim 2, characterized in that: In step (1), the acid-binding agent is pyridine or triethylamine, and the molar ratio of 2,2-bishydroxymethyl-1,3-propanediol to the acid-binding agent is 1:(12-16).

4. A process for the preparation of a quadruple structured emulsifier for developer according to claim 2, characterized in that: In step (2), the hydrolysis and dechlorination is carried out by immersing the intermediate product I in a high-pressure kettle at 220 DEG C for 2 hours using 4% NaOH aqueous solution.

5. A process for the preparation of a quaternary structured emulsifier for developer according to claim 2, characterized in that: In step (2), the mass ratio of the sodium ethoxide ethanol solution to the intermediate product I is 4:1, and the mass concentration of the sodium ethoxide ethanol solution is 95%.

6. Use of the emulsifier with tetradentate structure according to claim 1 in preparation of a CF process developing solution.

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