An end-capped polyether containing a bridged ring structure for a developer

Abstract

The application discloses a capped polyether containing a bridged ring structure and application thereof. The capped polyether is a surfactant containing a bridged ring structure, which is prepared by the following steps: 1-methyl-4-(1-methylethyl)-1,3-hexadiene and cis-butenediol are subjected to a Diels-Alder reaction to generate a diol intermediate A containing a bridged ring structure, then the diol intermediate A is subjected to polymerization reactions with propylene oxide and ethylene oxide under high pressure conditions to generate a gemini type polyether containing a bridged ring structure, and finally the obtained polyether is subjected to a reaction with acetic anhydride. The capped polyether containing a bridged ring structure prepared by the application has a good dispersing effect on photoresist, the gemini type structure features a lower CMC concentration, and thus the capped polyether has a better application in a developing solution.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of surfactant preparation, and particularly relates to a capped polyether containing a bridged ring structure for a developing solution and a preparation method thereof. BACKGROUND

[0002] In the manufacturing process in the field of flat panel display and semiconductor, multiple processes are needed, some of which involve the development of negative photoresist. The photoetching process generally includes coating, pre-baking, exposure, development and post-baking. After the pre-baking process, the photoresist solvent is removed, then different regions are exposed by a mask, the exposed regions are removed by an alkaline developing solution, and the unexposed regions are retained to obtain a corresponding pattern.

[0003] Commonly used in the developing solution is an organic or inorganic alkaline substance as the main component for dissolving the photoresist. However, a solution composed of water and alkali alone cannot meet the requirements. The main reason is that the surface tension is too high, and the developing solution cannot quickly and uniformly spread to the surface of the entire photoresist, resulting in uneven and incomplete development, local overdevelopment and blurred pattern edges, and the like. At the same time, the dissolved photoresist has poor dispersibility in water and is easy to aggregate into clusters and be adsorbed on the photoresist pattern after development, which can cause defects or block the filtration system.

[0004] The capped polyether containing a bridged ring structure for a developing solution prepared by the application has a bridged ring structure similar to the structure of the photoresist, which can play a good dispersion role; the gemini structure makes it have a lower CMC concentration, which can effectively reduce the surface tension of the solution, and has a good application prospect in the developing solution. SUMMARY

[0005] In order to enrich the types of surfactants specially used in the field of developing solution manufacturing, the application provides a capped polyether containing a bridged ring structure for a developing solution and a preparation method thereof.

[0006] To achieve the above object, the application adopts the following technical scheme:

[0007] A capped polyether containing a bridged ring structure has the following chemical structure:

[0008] wherein m and n are integers of 0-200 and not 0.

[0009] The preparation process of the capped polyether containing a bridged ring structure is as follows:

[0010] The preparation thereof includes the following steps:

[0011] (1) 1-methyl-4-(1-methyl ethyl)-1,3-hexadiene and butenediol are mixed in dichloromethane as solvent under the condition of low-temperature condensation water at 10℃, and then the mixture is refluxed at 40℃ for 6-12 h to obtain intermediate product A;

[0012] (2) A catalyst is added to the obtained intermediate product A, and then the mixture is treated by dehydration at a temperature of 130-150℃ for 30 min while the system gas is replaced by nitrogen for 3 times. Then a small amount of propylene oxide is added, and the mixture is induced to react at 140℃ under a pressure of less than 0.3 MPa. When the reaction pressure obviously decreases and the temperature sharply increases, the propylene oxide is continuously added, and the mixture is reacted at a temperature of 130-160℃ under a pressure of less than 0.3 MPa until the reaction pressure no longer decreases. Then the mixture is continuously heated for 30 min, and the unreacted monomer is removed by pressure reduction to obtain a polyether containing a bridged ring structure.

[0013] (3) A small amount of ethylene oxide is added to the obtained intermediate product B, and the mixture is induced to react at 140℃ under a pressure of less than 0.3 MPa. When the pressure obviously decreases and the temperature sharply increases, the ethylene oxide is continuously added, and the mixture is reacted at a temperature of 130-160℃ under a pressure of less than 0.3 MPa until the reaction pressure no longer decreases. Then the mixture is continuously heated for 30 min, and the unreacted monomer is removed by pressure reduction to obtain a polyether containing a bridged ring structure.

[0014] (4) The polyether containing a bridged ring structure and acetic anhydride are stirred and mixed, and then the mixture is reacted at 130℃ for 3 h. After the reaction is completed, the temperature is lowered to 120℃, and the unreacted substances are removed by distillation under reduced pressure to obtain a capped polyether containing a bridged ring structure.

[0015] Further, the molar ratio of 1-methyl-4-(1-methyl ethyl)-1,3-hexadiene to butenediol used in step (1) is 1:(1-1.2).

[0016] Further, the amount of the catalyst added in step (2) is 50-100 ppm based on the total mass of 1-methyl-4-(1-methyl ethyl)-1,3-hexadiene, butenediol, and the used ethylene oxide and propylene oxide.

[0017] Further, the catalyst is prepared by mixing an alkali catalyst and a double metal cyanide complex catalyst at a mass ratio of 1:1. The alkali catalyst is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium ethoxide, and potassium methoxide. The double metal cyanide complex catalyst is Zn3[CO(CN)6]2·0.08 ZnCl2·1 H2O·1 DMC, Zn3[CO(CN)6]2·0.08 ZnCl2·2.2 Cu(NO3)2·5 H2O.

[0018] Further, the molar ratio of 1-methyl-4-(1-methylethyl)-1,3-hexadiene to propylene oxide, ethylene oxide used is 1:(25-60):(12-25).

[0019] Further, the molar ratio of the polyether containing bridged ring structure to acetic anhydride used in step (4) is 1:(2-5).

[0020] The prepared polyether containing bridged ring structure can be used to prepare a developing solution.

[0021] Compared with the prior art, the present application has the following advantages and beneficial effects:

[0022] (1) The prepared polyether contains bridged ring structure in the molecule, which is similar to the structure of photoresist, and according to the principle of similar dissolves similar, the dispersibility of the polyether to photoresist is better;

[0023] (2) The prepared polyether is a gemini type polyether, that is, one molecule contains two hydrophilic groups and two hydrophobic groups, and the distance between them can be shortened by using the strong force of covalent bond, so that they can be arranged more closely on the surface of the liquid, thereby the surface tension of water can be more effectively reduced;

[0024] (3) The prepared polyether has better compatibility, and no precipitation occurs in a 15% sodium hydroxide aqueous solution, so that it can be used to prepare a high-concentration developing solution, thereby greatly reducing the production and transportation costs. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 The FT-IR graph of the prepared polyether containing bridged ring structure of Example 1.

[0026] Figure 2 The surface tension test graph of the prepared polyether containing bridged ring structure of Examples 1-5. DETAILED DESCRIPTION

[0027] 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.

[0028] Example 1

[0029] (1) 1.36 kg (10 mol) of 1-methyl-4-(1-methylethyl)-1,3-hexadiene and 0.88 kg (10 mol) of cis-butenediol were added under the condition of 10℃ low-temperature condensation water, 3 L of dichloromethane was added as a solvent, and the reaction was carried out at 40℃ under reflux for 12 h to obtain an intermediate product A;

[0030] (2) 1.12 kg (5 mol) of the intermediate product A and 0.1 g of sodium hydroxide, 0.1 g of Zn3[CO(CN)6]2·0.08ZnCl2·1H2O·1DMF were added into a reactor, heated to 150°C for 30 min of dehydration, while the system gas was replaced by nitrogen for 3 times, then 100 g (1.72 mol) of propylene oxide was added, and the temperature was maintained at 140°C and the pressure was less than 0.3 MPa for the induction reaction, when the reactor pressure decreased significantly and the temperature rose sharply, 7.55 kg (130 mol) of propylene oxide was continuously added, and the temperature was maintained at 130-160°C and the pressure was controlled to be less than 0.3 MPa for the reaction, until the reactor pressure no longer decreased, and then the reaction was continued for 30 min, to obtain the intermediate product B;

[0031] (3) The temperature was maintained at 140°C, and 100 g (2.27 mol) of ethylene oxide was continuously added into the reactor, and the pressure was maintained to be less than 0.3 MPa for the induction reaction, when the temperature rose sharply and the pressure decreased significantly, 5 kg (113.5 mol) of ethylene oxide was continuously added, and the temperature was maintained at 130-160°C and the pressure was maintained to be less than 0.3 MPa for the reaction, until the reactor pressure no longer decreased, and then the reaction was continued for 30 min, and the unreacted monomers were removed by reducing the pressure, to obtain a polyether containing a bridged ring structure;

[0032] (4) 1.2 kg (0.5 mol) of the polyether containing a bridged ring structure and 0.255 kg (2.21 mol) of acetic anhydride were added into a reactor equipped with a stirrer and a thermometer, and stirred and mixed, and heated to 130°C for 3 h of reaction, after the reaction was completed, the temperature was lowered to 120°C, and the unreacted substances were removed by distillation under reduced pressure, to obtain a capped polyether containing a bridged ring structure.

[0033] Example 2

[0034] (1) 1.36 kg (10 mol) of 1-methyl-4-(1-methylethyl)-1,3-hexadiene and 1.056 kg (12 mol) of cis-butenediol were added at 10°C under the condition of low-temperature condensation water, and 3 L of dichloromethane was added as a solvent, and the reaction was carried out at 40°C for 10 h of reflux, to obtain the intermediate product A;

[0035] (2) Put 1.12 kg (5 mol) of intermediate product A, 0.1 g of potassium methoxide and 0.1 g of Zn3[CO(CN)6]2·0.08 ZnCl2·2.2 Cu(NO3)2·5 H2O into a reactor, heat to 150°C for 30 min, replace the system gas with nitrogen for 3 times, then add 150 g (2.58 mol) of propylene oxide, maintain the temperature at 140°C and the pressure less than 0.3 MPa for induction reaction, when the reactor pressure decreases significantly and the temperature rises sharply, continue to add 7.2 kg (123.97 mol) of propylene oxide, maintain the temperature at 130-160°C and the pressure less than 0.3 MPa for reaction, until the reactor pressure no longer decreases, continue to maintain the temperature for 30 min, to obtain intermediate product B;

[0036] (3) Maintain the temperature at 140°C, continue to add 100 g (2.27 mol) of ethylene oxide into the reactor, maintain the pressure less than 0.3 MPa for induction reaction, when the temperature rises sharply and the pressure decreases significantly, continue to add 3.5 kg (79.46 mol) of ethylene oxide, maintain the temperature at 130-160°C and the pressure less than 0.3 MPa for reaction, until the reactor pressure no longer decreases, continue to maintain the temperature for 30 min, remove the unreacted monomers under reduced pressure, to obtain a polyether containing a bridged ring structure;

[0037] (4) Put 1.25 kg (0.5 mol) of the polyether containing a bridged ring structure and 0.204 kg (2 mol) of acetic anhydride into a reactor equipped with a stirrer and a thermometer, mix and stir, heat to 130°C for 3 h, after the reaction is completed, cool to 120°C, remove the unreacted substances by distillation under reduced pressure, to obtain a capped polyether containing a bridged ring structure.

[0038] Example 3

[0039] (1) Add 1.36 kg (10 mol) of 1-methyl-4-(1-methylethyl)-1,3-hexadiene and 1.056 kg (12 mol) of cis-butenediol at 10°C under the condition of low-temperature condensation water, add 3 L of dichloromethane as a solvent, and reflux at 40°C for 10 h to obtain intermediate product A;

[0040] (2) Put 1.12 kg (5 mol) of intermediate product A, 0.1 g of sodium ethoxide and 0.1 g of Zn3[CO(CN)6]2·0.08ZnCl2·1 H2O·1 DMF into a reactor, heat to 150°C for 30 min, replace the system gas with nitrogen for 3 times, then add 150 g (2.58 mol) of propylene oxide, keep the temperature at 140°C and the pressure less than 0.3 MPa for induction reaction, when the reactor pressure decreases obviously and the temperature rises sharply, continue to add 17.4 kg (300 mol) of propylene oxide, keep the temperature at 130-160°C and the pressure less than 0.3 MPa for reaction, until the reactor pressure no longer decreases, continue to keep the temperature for 30 min, to obtain intermediate product B;

[0041] (3) Keep the temperature at 140°C, continue to add 100 g (2.27 mol) of ethylene oxide into the reactor, keep the pressure less than 0.3 MPa for induction reaction, when the temperature rises sharply and the pressure decreases obviously, continue to add 3.5 kg (79.45 mol) of ethylene oxide, keep the temperature at 130-160°C and the pressure less than 0.3 MPa for reaction, until the reactor pressure no longer decreases, continue to keep the temperature for 30 min, remove the unreacted monomers under reduced pressure, to obtain a polyether containing a bridged ring structure;

[0042] (4) Put 1.2 kg (0.5 mol) of the polyether containing a bridged ring structure and 0.102 kg (1 mol) of acetic anhydride into a reactor equipped with a stirrer and a thermometer, mix and stir, heat to 130°C for 3 h, after the reaction is completed, cool to 120°C, remove the unreacted substances by distillation under reduced pressure, to obtain a capped polyether containing a bridged ring structure.

[0043] Example 4

[0044] The mass of propylene oxide and ethylene oxide during polymerization is controlled to be 10 kg (172.18 mol) and 4 kg (90.81 mol) respectively, and the rest of the conditions are the same as in Example 1.

[0045] Example 5

[0046] The mass of propylene oxide and ethylene oxide during polymerization is controlled to be 8 kg (137.74 mol) and 3 kg (68.10 mol) respectively, and the rest of the conditions are the same as in Example 2.

[0047] Figure 1The surface tension test results of the capped polyether containing bridged ring structure prepared in Examples 1-5 are shown in the figure. As can be seen from the figure, the capped polyether containing bridged ring structure prepared in the five examples all have a low CMC concentration, and when the concentration reaches above the CMC, the surface tension of water can be reduced to 27-29 mN / m, which is more excellent than the performance of the surfactants on the market.

[0048] Application Examples:

[0049] 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 capped polyether containing bridged ring structure 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 developer prepared by not adding the capped polyether and using the uncapped polyether containing bridged ring structure as a dispersant was used as a comparison. The state of the obtained developer is shown in Table 1.

[0050] Table 1

[0051]

[0052] Performance Test:

[0053] In order to verify the performance of the above developer, the following experimental scheme was used for determination.

[0054] 1. Preparation of glass substrate

[0055] 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 plate was transferred to the glass substrate by exposure.

[0056] 2. Development test

[0057] The prepared developer was diluted 20-60 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 how long the service life of the developer was. The results are shown in Table 2.

[0058] Table 2

[0059]

[0060] From the results of Table 2, it can be seen that the developer prepared in the examples is clear and transparent, stable in properties, and unlikely to precipitate, and can achieve the advantages of suitable developing speed, clear pattern, complete edge, no photoresist residue, and long service life.

[0061] The above description is only the preferred embodiment of the present application, and any equivalent changes and modifications made within the scope of the patent application of the present application shall be covered by the present application.

Claims

1. A method for preparing a blocked polyether containing a bridged ring structure, characterized in that: The following steps are involved: (1) Using dichloromethane as solvent, 1-methyl-4-(1-methylethyl)-1,3-hexadiene and butenediol were mixed under low-temperature condensation conditions at 10°C, and refluxed at 40°C for 6-12 h to obtain intermediate product A; (2) Add a catalyst to the intermediate product A, maintain the temperature at 130-150 ° C for 30 min, and replace the system gas with nitrogen three times. Then add a small amount of propylene oxide and induce the reaction at 140 ° C and a pressure of less than 0.3 MPa. When the reaction pressure drops significantly and the temperature rises sharply, continue to add propylene oxide and maintain the temperature at 130-160 ° C and a pressure of less than 0.3 MPa to react until the reaction pressure no longer decreases. Continue to keep the temperature for 30 min to obtain the intermediate product B. (3) Add a small amount of ethylene oxide to the intermediate product B, and induce the reaction at 140°C and a pressure of less than 0.3 MPa. When the pressure drops significantly and the temperature rises sharply, continue to add ethylene oxide, and keep the temperature at 130-160°C and the pressure less than 0.3 MPa to react until the reaction pressure no longer decreases. Continue to keep the temperature and react for 30 minutes, and remove the unreacted monomer under reduced pressure to obtain a polyether containing a bridged ring structure. (4) The polyether containing a bridged ring structure and acetic anhydride were stirred and mixed, and reacted at 130°C for 3 hours. After the reaction was completed, the temperature was lowered to 120°C, and the unreacted substances were removed by vacuum distillation to obtain a blocked polyether containing a bridged ring structure, the chemical structure of which is as follows: , where m and n are integers ranging from 0 to 200 and are not 0.

2. The method for preparing a blocked polyether containing a bridged ring structure according to claim 1, wherein: The molar ratio of 1-methyl-4-(1-methylethyl)-1,3-hexadiene to cis-1-butenediol used in step (1) is 1:(1-1.2).

3. The method for preparing a blocked polyether containing a bridged ring structure according to claim 1, wherein: The amount of catalyst added in step (2) is 50-100 ppm based on the total mass of 1-methyl-4-(1-methylethyl)-1,3-hexadiene, butenediol, ethylene oxide and propylene oxide used.

4. The method for preparing a blocked polyether containing a bridged ring structure according to claim 1 or 3, characterized in that: The catalyst is prepared by mixing an alkali catalyst and a double metal cyanide complex catalyst in a mass ratio of 1:

1.

5. The method for preparing a blocked polyether containing a bridged ring structure according to claim 4, wherein: The alkaline catalyst is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium ethoxide, and potassium methoxide.

6. The method for preparing a blocked polyether containing a bridged ring structure according to claim 4, wherein: The double metal cyanide complex catalyst is Zn3[CO(CN)6]2·0.08 ZnCl2·1 H2O·1 DMC, Zn3[CO(CN)6]2·0.08 ZnCl2·2.2 Cu(NO3)2·5 H2O.

7. The method for preparing a blocked polyether containing a bridged ring structure according to claim 1, wherein: The molar ratio of 1-methyl-4-(1-methylethyl)-1,3-hexadiene to propylene oxide and ethylene oxide is 1:(25-60):(12-25).

8. The method for preparing a blocked polyether containing a bridged ring structure according to claim 1, wherein: The molar ratio of the polyether containing a bridged ring structure to acetic anhydride used in step (4) is 1:(2-5).

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