Method for detecting moisture of 2, 3, 4-trihydroxybenzophenone 1, 2-diazido naphthoquinone-5-sulfonate

Abstract

The invention provides a method for detecting the content of water in 2, 3, 4-trihydroxy benzophenone 1, 2-diazido naphthoquinone-5-sulfonate, which comprises the following steps: pretreating a sample by using an external dissolution method, measuring the content of water in 2, 3, 4-trihydroxy benzophenone 1, 2-diazido naphthoquinone-5-sulfonate by using a Karl Fischer Coulomb method, and measuring the content of water in 2, 3, 4-trihydroxy benzophenone 1, 2-diazido naphthoquinone-5-sulfonate by using a Karl Fischer Coulomb method. The Karl-Fischer reagent comprises the following components in percentage by mass: 70% of methanol, 10% of diethanol amine, 10% of imidazole, 5% of sulfur dioxide and 5% of hydriodic acid, a sample needs to be pretreated by an external dissolution method before moisture detection, the moisture content m1 of the measured sample, the moisture content m2 of a blank solvent, the weight x1 of the solvent and the weight x2 of the sample are recorded and measured respectively, correction is performed by using a correction formula, and the content of the sample is measured. Finally, the moisture determination of the 2, 3, 4-trihydroxy benzophenone 1, 2-diazido naphthoquinone-5-sulfonate is realized.

Description

Technical Field

[0001] The invention belongs to the technical field of water detection methods for photoinitiators, and specifically relates to a water detection method for 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate. Background Art

[0002] 2,3,4-Trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate is a chemical substance with the chemical formula C 43 H 22 N 6 O 13 S 3 , with a molecular weight of 926.86200. This compound is commonly used as a photoinitiator, especially as a raw material for I-line and G-line photoresists used in the semiconductor and FPD (flat panel display) industries. Photoinitiators play an important role in the field of photocuring. They can undergo chemical reactions under the irradiation of light of a specific wavelength to initiate monomer polymerization, thereby achieving rapid curing. In the semiconductor manufacturing process, photoresists are used to form fine patterns on silicon wafers, and photoinitiators are the core components that realize the exposure and development process of photoresists.

[0003] Photoresists are widely used in the fields of microelectronics, micromechanics and printing. 2,3,4-Trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate is a diazonaphthoquinone positive photoresist. Due to its advantages of high resolution, strong resistance to dry etching, good heat resistance and convenient degumming, it meets the needs of increasing integration of large-scale integrated circuits and the development of line width of graphics from micrometers to submicrometers, and its usage is increasing.

[0004] Too high moisture content in the photoinitiator will have an adverse effect on the photocuring process. Moisture will affect the chemical structure of the photoinitiator, causing it to fail, thereby affecting the efficiency of the photocuring reaction and the performance of the final product. Therefore, controlling the moisture content of the photoinitiator is an important link in ensuring the quality of photocurable products. Since 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate is a solid sample at room temperature, it cannot be directly measured in the coulometric titration cup, and a cassette furnace-Karl Fischer titrator is used to measure moisture.

[0005] The combined determination method of the cassette furnace and Karl Fischer titrator is suitable for samples that will separate from water at higher temperatures, are difficult to dissolve, or react easily with Karl Fischer reagents. Weigh the sample to be tested and put it into a small sample bottle sealed with a diaphragm and place it on the sample tray. Set the temperature of the cassette furnace to heat the sample bottle. While heating, a sleeve needle will penetrate the diaphragm from above the sample bottle, and the dry carrier gas will enter the bottle and transport the evaporated water to the sample pool of the moisture meter for detection. However, there are still some disadvantages when detecting the moisture content of the sample: 1. It takes a long time, resulting in inaccurate measurement results, and a specific correction method needs to be adopted, which increases the difficulty of operation; 2. The carrier gas flow rate has an important influence on the transmission and reaction of moisture. An inappropriate flow rate will affect the determination of the titration end point; 3. The sample contains bound water or crystal water, and direct heating may not be able to completely release all the moisture, resulting in a low measurement result; 4. When the ambient temperature is low, the moisture carried away by the carrier gas is easy to condense on the tube wall, resulting in a low moisture measurement; 5. If the carrier gas flow rate is set too high, some moisture may escape without participating in the reaction, resulting in a low test result.

[0006] The external dissolution pretreatment method used in this paper can not only ensure that the water is evenly dispersed in the solution, but also obtain the water detection results more quickly. Compared with the Karl Fischer drying furnace water measurement, it will not cause experimental errors and other measurement problems due to the carrier gas, and provide more accurate and reliable water content measurement results. Summary of the invention

[0007] The technical problem to be solved by the present invention is to provide a method for detecting moisture in 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate.

[0008] In order to solve the above technical problems, the present invention adopts the following technical solution: a method for detecting the moisture content of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate, which uses an external dissolution method to pretreat the sample and uses the Karl Fischer Coulometry method to measure the moisture content of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate. The specific detection method is as follows: Step 1: Add fresh Karl Fischer reagent to the coulometric titrator, start pre-titration, and wait for the water in the Karl Fischer reagent to be removed and the instrument to reach standby mode; Step 2: In standby mode, use a 10 ml syringe to draw 1-2 ml of anhydrous Karl Fischer reagent from the titration cup, shake the syringe to eliminate the moisture on the inner wall of the syringe and the syringe needle, and discard the Karl Fischer reagent used to rinse the syringe.

[0009] Step 3: Take two diaphragm-sealed and dried vials, add the sample into one of the vials, mark it as sample 1, and record the sample weight as m. 1, mark the other vial as sample 2, and record the sample weight as m 2 , seal it. Use the same syringe to draw 5-10ml of anhydrous Karl Fischer reagent, inject the Karl Fischer reagent into two sealed vials respectively, and record the weight of anhydrous Karl Fischer reagent as m 2 , shake the vial to dissolve the sample and the water in the sample in the anhydrous Karl Fischer reagent, and take a certain amount of solution from sample 1 and 2 for measurement. The measurement result of sample 1 is marked as x 1 , the result of sample 2 is x 2 , repeat the above operation three times and perform parallel experiments.

[0010] Step 4: Convert the m measured above 1 、m 2 、x 1 、x 2 The formula is used for correction to obtain accurate moisture detection results of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate.

[0011] In step 1, the Karl Fischer reagent is composed of 50-70% methanol, 5-15% diethanolamine, 5-15% imidazole, 3-10% sulfur dioxide, and 3-10% hydroiodic acid by mass fraction. As a preferred embodiment, 100 ml of Karl Fischer reagent is added, and a reagent composed of 70% methanol, 10% diethanolamine, 10% imidazole, 5% sulfur dioxide, and 5% hydroiodic acid by mass fraction is selected.

[0012] In step one, the type of instrument detection method selected is: Coulometric method KF; maximum starting drift: 25μg / min; mixing time: 60s; electrode polarization current: 5-10μA; generating electrode current: 200-400mA; stirring speed: 1500rpm / min; control end point: 100mV; control zone: 250mV; termination drift value: 3μg / min.

[0013] In some embodiments, the electrode polarization current is any one of 5μA, 6μA, 7μA, 8μA, 9μA, and 10μA.

[0014] The generating electrode current is any one of 200 mA, 250 mA, 300 mA, 350 mA, and 400 mA.

[0015] In step 2, rinsing the syringe should be repeated three times.

[0016] In step three, the injection volume is about 0.5 g each time. Injecting more samples will waste Karl Fischer reagent and reduce detection efficiency, while injecting less samples will lead to larger errors.

[0017] In step 3, the ratio of the sample pre-treated by the external dissolution method is: Sample size 2g Anhydrous Karl Fischer reagent 5ml In step 4, the correction formula is

[0018] m 1 : Measure the water content of the sample (%, ppm) m 2 : Water content of blank solvent (%, ppm) x 1 : Weight of solvent (g) x 2 : Sample weight (g) The beneficial effects of the present invention are as follows: a suitable moisture detection pretreatment method is selected for 2,3,4-trihydroxybenzophenone 1,2-naphthoquinonediazide-5-sulfonate, and the detection method is optimized, so that the moisture can be ensured to be evenly dispersed in the solution, and the moisture detection result can be obtained more quickly. Compared with the measurement of moisture in a Karl Fischer drying furnace, there will be no measurement difficulties such as experimental errors due to carrier gas, and a more accurate and reliable moisture content measurement result is provided. DETAILED DESCRIPTION

[0019] Example 1 Determination method using a combination of a furnace and a Karl Fischer titrator Weigh about 1g of sample (accurate to 0.1g) into the injection bottle, seal the injection bottle with a sealing film, and put the injection bottle into the corresponding position of the injector; at the same time, prepare an empty injection bottle without sample, and place the empty injection bottle in the "BLANK" position with a sealing film; in addition, place another empty injection bottle on the "zero position" of the injector for drift determination. Start the setting method, the instrument first performs drift determination, and after completion, the instrument prompts to enter the mass of the sample (the mass of the blank does not need to be entered), and then automatically runs the sequence to obtain the water content in the sample (the instrument automatically subtracts the water in the sample from the water in the blank and then divides it by the mass of the sample to obtain the water content in the sample).

[0020] Operating conditions: temperature of the cassette furnace autosampler: 230 ℃±1 ℃; heating time of the cassette furnace autosampler: 20 min; carrier gas flow rate: 45 mL / min; endpoint relative drift: 10 μg / min; extraction time: 5 min.

[0021] Table 1 Moisture determination results using a Karl Fischer oven combined with a Karl Fischer titrator

[0022] External dissolution pretreatment determination method Step 1: Set the parameters of the Karl Fischer titrator as follows: Coulometric method KF; Maximum initial drift: 25μg / min; Mixing time: 60s; Electrode polarization current: 5μA; Generating electrode current: 200mA; Stirring speed: 1500rpm / min; Control end point: 100mV; Control zone: 250mV; End drift value: 3μg / min. Then add 100ml of fresh Karl Fischer reagent to the coulometric titrator, start pre-titration, wait for the water in the Karl Fischer reagent to be removed, and the instrument reaches standby mode; Step 2: In standby mode, use a 10ml syringe to draw 1-2ml of anhydrous Karl Fischer reagent from the titration cup, shake the syringe to eliminate the moisture on the inner wall of the syringe and the syringe needle, discard the Karl Fischer reagent used to rinse the syringe, and repeat the above operation three times.

[0023] Step 3: Take two diaphragm-sealed and dried vials, add 2 g of sample into one of the vials, mark it as sample 1, and record the sample weight as m 1 , mark the other vial as sample 2, and record the sample weight as m 2 Use the same syringe to draw anhydrous Karl Fischer reagent and inject 5 ml of Karl Fischer reagent into two sealed vials respectively. Record the weight of anhydrous Karl Fischer reagent as m 2 , shake the vial to dissolve the water in the sample in the anhydrous Karl Fischer reagent, and take a certain amount of solution from sample 1 and 2 for measurement. The measurement result of sample 1 is marked as x 1 , the result of sample 2 is x 2 , repeat the above operation three times and perform parallel experiments.

[0024] Step 4: Convert the m measured above 1 、m 2 、x 1 、x 2 The following formula is used for correction to obtain accurate moisture detection results of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate.

[0025]

[0026] m 1 : Measure the water content of the sample (%, ppm) m 2 : Water content of blank solvent (%, ppm) x 1 : Weight of solvent (g) x 2 : Sample weight (g) Table 1 Moisture determination results

[0027] Table 2 Moisture determination results after correcting the formula

[0028] Example 2 Step 1: Set the parameters of the Karl Fischer titrator as follows: Coulometric method KF; Maximum initial drift: 25μg / min; Mixing time: 60s; Electrode polarization current: 5μA; Generating electrode current: 400mA; Stirring speed: 1500rpm / min; Control end point: 100mV; Control zone: 250mV; End drift value: 3μg / min. Then add 100ml of fresh Karl Fischer reagent to the coulometric titrator, start pre-titration, wait for the water in the Karl Fischer reagent to be removed, and the instrument reaches standby mode; Step 2: In standby mode, use a 10ml syringe to draw 1-2ml of anhydrous Karl Fischer reagent from the titration cup, shake the syringe to eliminate the moisture on the inner wall of the syringe and the syringe needle, discard the Karl Fischer reagent used to rinse the syringe, and repeat the above operation three times.

[0029] Step 3: Take two diaphragm-sealed and dried vials, add 2 g of sample into one of the vials, mark it as sample 1, and record the sample weight as m 1 , mark the other vial as sample 2, and record the sample weight as m 2 Use the same syringe to draw anhydrous Karl Fischer reagent and inject 5 ml of Karl Fischer reagent into two sealed vials respectively. Record the weight of anhydrous Karl Fischer reagent as m 2 , shake the vial to dissolve the water in the sample in the anhydrous Karl Fischer reagent, and take a certain amount of solution from sample 1 and 2 for measurement. The measurement result of sample 1 is marked as x 1 , the result of sample 2 is x 2 , repeat the above operation three times and perform parallel experiments.

[0030] Step 4: Convert the m measured above 1 、m 2 、x 1 、x 2 The following formula is used for correction to obtain accurate moisture detection results of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate.

[0031]

[0032] m 1 : Measure the water content of the sample (%, ppm) m 2 : Water content of blank solvent (%, ppm) x 1 : Weight of solvent (g) x 2 : Sample weight (g) Table 1 Moisture determination results

[0033] Table 2 Moisture determination results after correcting the formula

[0034] Example 3 Step 1: Set the parameters of the Karl Fischer titrator as follows: Coulometric method KF; Maximum initial drift: 25μg / min; Mixing time: 60s; Electrode polarization current: 10μA; Generating electrode current: 200mA; Stirring speed: 1500rpm / min; Control end point: 100mV; Control zone: 250mV; End drift value: 3μg / min. Then add 100ml of fresh Karl Fischer reagent to the coulometric titrator, start pre-titration, wait for the water in the Karl Fischer reagent to be removed, and the instrument reaches standby mode; Step 2: In standby mode, use a 10ml syringe to draw 1-2ml of anhydrous Karl Fischer reagent from the titration cup, shake the syringe to eliminate the moisture on the inner wall of the syringe and the syringe needle, discard the Karl Fischer reagent used to rinse the syringe, and repeat the above operation three times.

[0035] Step 3: Take two diaphragm-sealed and dried vials, add 2 g of sample into one of the vials, mark it as sample 1, and record the sample weight as m 1 , mark the other vial as sample 2, and record the sample weight as m 2 Use the same syringe to draw anhydrous Karl Fischer reagent and inject 5 ml of Karl Fischer reagent into two sealed vials respectively. Record the weight of anhydrous Karl Fischer reagent as m 2 , shake the vial to dissolve the water in the sample in the anhydrous Karl Fischer reagent, and take a certain amount of solution from sample 1 and 2 for measurement. The measurement result of sample 1 is marked as x 1 , the result of sample 2 is x 2 , repeat the above operation three times and perform parallel experiments.

[0036] Step 4: Convert the m measured above 1 、m 2 、x 1 、x 2 The following formula is used for correction to obtain accurate moisture detection results of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate.

[0037]

[0038] m 1 : Measure the water content of the sample (%, ppm) m 2 : Water content of blank solvent (%, ppm) x 1 : Weight of solvent (g) x 2 : Sample weight (g) Table 1 Moisture determination results

[0039] Table 2 Moisture determination results after correcting the formula

[0040] Example 4 Step 1: Set the parameters of the Karl Fischer titrator as follows: Coulometric method KF; Maximum initial drift: 25μg / min; Mixing time: 60s; Electrode polarization current: 10μA; Generating electrode current: 400mA; Stirring speed: 1500rpm / min; Control end point: 100mV; Control zone: 250mV; End drift value: 3μg / min. Then add 100ml of fresh Karl Fischer reagent to the coulometric titrator, start pre-titration, wait for the water in the Karl Fischer reagent to be removed, and the instrument reaches standby mode; Step 2: In standby mode, use a 10ml syringe to draw 1-2ml of anhydrous Karl Fischer reagent from the titration cup, shake the syringe to eliminate the moisture on the inner wall of the syringe and the syringe needle, discard the Karl Fischer reagent used to rinse the syringe, and repeat the above operation three times.

[0041] Step 3: Take two diaphragm-sealed and dried vials, add 2 g of sample into one of the vials, mark it as sample 1, and record the sample weight as m 1 , mark the other vial as sample 2, and record the sample weight as m 2 Use the same syringe to draw anhydrous Karl Fischer reagent and inject 5 ml of Karl Fischer reagent into two sealed vials respectively. Record the weight of anhydrous Karl Fischer reagent as m 2 , shake the vial to dissolve the water in the sample in the anhydrous Karl Fischer reagent, and take a certain amount of solution from sample 1 and 2 for measurement. The measurement result of sample 1 is marked as x 1 , the result of sample 2 is x 2 , repeat the above operation three times and perform parallel experiments.

[0042] Step 4: Convert the m measured above 1 、m 2、x 1 、x 2 The following formula is used for correction to obtain accurate moisture detection results of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate.

[0043]

[0044] m 1 : Measure the water content of the sample (%, ppm) m 2 : Water content of blank solvent (%, ppm) x 1 : Weight of solvent (g) x 2 : Sample weight (g) Table 1 Moisture determination results

[0045] Table 2 Moisture determination results after correcting the formula

[0046] The moisture test results of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate measured by the external dissolution pretreatment determination method are more stable than those measured by the combined determination method of the cassette furnace and Karl Fischer titrator. The crystal water in the sample is completely released. The measured results are higher than those of the combined determination method of the cassette furnace and Karl Fischer titrator, but they are closer to the true values. By changing the electrode polarization current and the generating electrode current parameters of the Karl Fischer titrator, it is determined that the electrode polarization current is 5μA and the generating electrode current is 400mA, which is the best parameter, and the measured moisture is the same as the true value.

[0047] The above-mentioned embodiments are only preferred technical solutions of the present invention and should not be regarded as limitations of the present invention. The embodiments and features in the embodiments of the present application can be arbitrarily combined with each other without conflict. The protection scope of the present invention shall be the technical solutions recorded in the claims, including the equivalent replacement solutions of the technical features in the technical solutions recorded in the claims. That is, equivalent replacement improvements within this scope are also within the protection scope of the present invention.

Claims

1. A method for detecting moisture in 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate, characterized in that: The detection method is as follows: Step 1: Add fresh Karl Fischer reagent to the coulometric titrator, start pre-titration, and wait for the water in the Karl Fischer reagent to be removed and the instrument to reach standby mode; Step 2: In standby mode, draw 1-2 ml of anhydrous Karl Fischer reagent and inject it into the syringe to eliminate the moisture on the inner wall of the syringe and the syringe needle; Step 3: Take two vials sealed with diaphragms and dried, add the sample into one of the vials, mark it as sample 1, record the sample weight as m1, mark the other vial as sample 2, record the sample weight as m2, and seal it; use the same syringe to absorb 5-10ml of anhydrous Karl Fischer reagent, inject the Karl Fischer reagent into the two sealed vials respectively, record the weight of the anhydrous Karl Fischer reagent as m2, shake the vials to dissolve the sample and the water in the sample in the anhydrous Karl Fischer reagent, and draw a certain amount of solution from sample 1 and sample 2 respectively to check the water content. The measurement result of sample 1 is marked as x1, and the result of sample 2 is marked as x2. Repeat the above operation three times for parallel testing; Step 4: Use the formula to correct the above measured m1, m2, x1, and x2 to obtain an accurate moisture detection result of 2,3,4-trihydroxybenzophenone 1,2-diazide naphthoquinone-5-sulfonate.

2. The method for detecting moisture of 2,3,4-trihydroxybenzophenone 1,2-naphthoquinone diazide-5-sulfonate according to claim 1, characterized in that: The Karl Fischer reagent comprises 50-70% methanol, 5-15% diethanolamine, 5-15% imidazole, 3-10% sulfur dioxide and 3-10% hydroiodic acid by mass fraction.

3. The method for detecting moisture of 2,3,4-trihydroxybenzophenone 1,2-naphthoquinone diazide-5-sulfonate according to claim 1, characterized in that: The moisture content detection method is Coulometric KF; maximum initial drift: 25 μg / min; mixing time: 60 s; electrode polarization current: 5-10 μA; generating electrode current: 200-400 mA; stirring speed: 1500 rpm / min; control end point: 100 mV; Control area: 250mV; End drift value: 3μg / min.

4. A method for detecting moisture in 2,3,4-trihydroxybenzophenone 1,2-naphthoquinone diazide-5-sulfonate according to claim 1, characterized in that: The ratio of samples pretreated by external dissolution method is: Sample size 2g 5 ml of anhydrous Karl Fischer reagent.

5. The method for detecting moisture of 2,3,4-trihydroxybenzophenone 1,2-naphthoquinone diazide-5-sulfonate according to claim 1, characterized in that: The correction formula is: m1: measure the water content of the sample (%, ppm) m2: Water content of blank solvent (%, ppm) x1: weight of solvent (g) x2: weight of the sample (g).

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