Green color paste for color photoresist and application thereof

Abstract

This invention belongs to the field of photoresist technology, and relates to a green color paste for color photoresist and its application. The green color paste for color photoresist comprises the following components by weight: 10 parts green pigment; 12-18 parts acrylic resin; 8-12 parts dispersant; 0.1-0.6 parts synergist; and 60-70 parts propylene glycol methyl ether acetate. The green color paste for color photoresist of this invention contains a synergist grafted onto the green pigment as the main chain. This synergist has excellent solubility and dispersibility, and can be well adsorbed and bound to the surface of the green pigment. This results in more functional groups on the surface of the green pigment that interlink with the dispersant, increasing the binding affinity and preventing the green pigment from agglomerating. This improves the contrast and brightness of the color paste, thus meeting the requirements of the production line. Furthermore, it can reduce the amount of dispersant used, reduce subsequent development time, and improve the quality of the color photoresist.

Description

Technical Field

[0001] This invention belongs to the field of photoresist technology, and particularly relates to a green pigment for color photoresist and its application. Background Technology

[0002] The photoresist market for thin-film transistor liquid crystal displays (TFT-LCDs) is basically dominated by Japanese and South Korean companies, with a market share reaching 95%, and the technological barriers are high. The color paste market is also entirely monopolized by Japanese and South Korean companies; most of the raw materials for domestic photoresist production are imported from abroad, and the domestic manufacturing of color color pastes is still nonexistent.

[0003] With the downstream industrial chains such as semiconductors, printed circuit boards and panels shifting to China, and the progress of localization of LCD panel main materials, the domestic market demand for photoresist pigments is continuously increasing. To significantly reduce the cost of photoresist, it is necessary to break the foreign monopoly that has lasted for many years. The localization project of nano pigments and pigments is of great urgency and necessity.

[0004] The quality of color filters primarily depends on the performance of the photoresist and its coating process. Photoresist pigments, as colorants, are a major influencing factor. To fully utilize their tinting strength and vibrancy, and achieve good spectral characteristics, the pigment particles must be dispersed in the photoresist in a fine, uniform, and stable state. This mainly involves selecting high-grade organic pigments and employing efficient dispersion processes to obtain a fine-particle-size and stable pigment dispersion—the color paste. The dispersion state and particle size of the pigment determine whether the final coating has high contrast. However, high contrast cannot be achieved solely through the process; therefore, it is necessary to synthesize a suitable green color paste for the color photoresist to enhance contrast. Summary of the Invention

[0005] To address the shortcomings of the existing technology, this invention provides a green pigment for color photoresist and its application. The specific technical solution is as follows:

[0006] A green pigment for color photoresist comprises the following components in parts by weight:

[0007] 10 parts green pigment; 12-18 parts acrylic resin; 8-12 parts dispersant; 0.1-0.6 parts synergist; 60-70 parts propylene glycol methyl ether acetate;

[0008] The structure of the synergist is shown in formula (Ⅰ):

[0009]

[0010] When green pigment paste is used without the aforementioned synergist and only with a dispersant, more dispersant is often needed to ensure better dispersion of the green pigment and allow for bonding between the pigment surface and the dispersant. However, excessive dispersant usage can lead to longer development times or peeling during development, where the pigment paste developer becomes insoluble and peels off the glass slide in clumps, resulting in poor-quality color photoresist. The addition of the synergist in this invention can reduce the amount of dispersant used, shorten subsequent development time, and improve the quality of the color photoresist.

[0011] Furthermore, the green pigment is Pigment Green G58.

[0012] Furthermore, the preparation method of the synergist includes the following steps:

[0013] (1) The reaction of cyanuric chloride, p-aminobenzenesulfonic acid, and 3-diethylaminopropylamine yields product 1 with the structure of formula 1.

[0014]

[0015] (2) Pigment Green G58 was reacted with 2wt% fuming sulfuric acid to give product II with the structure of formula 2;

[0016]

[0017] (3) The product 1 and product 2 are reacted with 3-diethylaminopropylamine to obtain an synergist with the structure of formula (I).

[0018]

[0019] The synergist of this invention uses green pigment as the main chain for grafting. After grafting polymerization, the groups of pigment G58 have good solubility and dispersibility, and can be well adsorbed and bound to the surface of green pigment. This makes the surface of green pigment have more functional groups that are linked to the dispersant, increasing the binding to the dispersant and preventing the green pigment from agglomerating.

[0020] Further, in step (1), cyanuric chloride, p-aminosulfonic acid and 3-diethylaminopropylamine are added to pure water at 15-30℃ and reacted for 0.5-1.5h. The product is then filtered, repeatedly washed and dried in an oven to obtain product one.

[0021] Further, in step (1), the molar ratio of cyanuric chloride, p-aminosulfonic acid and 3-diethylaminopropylamine is 2:1:1, and the amount of pure water is 50 g / mmol cyanuric chloride.

[0022] Further, in step (2), pigment green G58 and 2wt% fuming sulfuric acid solution are stirred and reacted at room temperature for 2-4 hours to obtain a reaction solution. The reaction solution is added to cold methyl ethyl ketone and stirred for 20-40 minutes to obtain a precipitate. The precipitate is then washed and filtered with methyl ethyl ketone to obtain a filter cake. The filter cake is then dried to obtain product two.

[0023] Further, in step (2), the mass ratio of pigment green G58 to 2wt% fuming sulfuric acid solution is (1-2):1.

[0024] Further, in step (3), product 2 is added to N,N-dimethylformamide, and thionyl chloride is added under stirring at 50-70°C. After stirring for 5-7 hours, the reaction solution is injected into an ice-water mixture to obtain a precipitate. The precipitate is filtered and the filter cake is washed with ice water. The filter cake is added to a mixed solution of ice, water, product 1 and 3-diethylaminopropylamine. The mixture is heated to 50-70°C, stirred for 80-100 minutes, filtered and dried.

[0025] Furthermore, in step (3), the mass ratio of product 2, product 1 and 3-diethylaminopropylamine solution is 1:(3-4):(2-3).

[0026] A second objective of this invention is to provide the application of the aforementioned green pigment for color photoresist in the preparation of color photoresist.

[0027] The beneficial effects of this invention are as follows:

[0028] This invention relates to an enhancer for green pigment paste used in color photoresists, which prevents the green pigment from agglomerating, thereby improving the contrast and brightness of the pigment paste to meet production line requirements. The addition of this enhancer can also reduce the amount of dispersant used, reduce subsequent development time, and improve the quality of color photoresists. Detailed Implementation

[0029] The principles and features of the present invention are described below with reference to examples. The examples are only used to explain the present invention and are not intended to limit the scope of the present invention.

[0030] Pigment Green G58: CAS No. 1143572-73-9, Molecular Formula: C 20 H 16 N2O2 molecular weight: 361.35.

[0031]

[0032] Cyanuron chloride: CAS: 108-77-0, molecular formula: C3Cl3N3, molecular weight: 184.41.

[0033]

[0034] p-Aminobenzenesulfonic acid: CAS: 121-57-3, molecular formula: C6H7NO3S, molecular weight: 173.19.

[0035]

[0036] 3-Diethylaminopropylamine: CAS: 104-78-9, Molecular formula: C7H 18 N2, molecular weight: 130.23.

[0037]

[0038] Methyl ethyl ketone: CAS: 78-93-3, molecular formula: C4H8O, molecular weight: 72.11.

[0039]

[0040] Fuming sulfuric acid CAS: 8014-95-7, molecular formula: H2SO4·xSO3, molecular weight: 98+x(80.06).

[0041] N,N-Dimethylformamide: CAS: 68-12-2, Molecular formula: C3H7NO, Molecular weight: 73.019.

[0042] PMA stands for propylene glycol methyl ether acetate, CAS number 108-65-6.

[0043] Resin (benzyl methacrylate / methacrylic acid = 70 / 30, molecular weight 12000; acid value 115, solid content 28%)

[0044] Dispersant: BYK-21116 (40% solids content) is a dispersant from BYK Chemical Company.

[0045] The preparation of the synergist described in this invention includes the following steps:

[0046] (1) Add 5 mmol of cyanuric chloride, 2.5 mmol of p-aminobenzenesulfonic acid and 2.5 mmol of 3-diethylaminopropylamine to 100 g of pure water, react at 20 °C for 1 h, filter the product, wash repeatedly, and then put it into an oven at 120 °C to dry, and obtain product one with the structure of Formula 1.

[0047] (2) At room temperature, 175g of C.I. Pigment Green G58 was added to 150g of 2wt% fuming sulfuric acid and stirred at room temperature for 3h to obtain a reaction solution. The reaction solution was added to 1500g of cold methyl ethyl ketone and stirred for 30min to obtain a precipitate. The precipitate was then washed and filtered with 5000g of methyl ethyl ketone to obtain a filter cake, which was then dried in an oven at 80℃ to obtain product two.

[0048] (3) Take 10g of product 2 and add it to 100g of N,N-dimethylformamide. Under the condition of stirring at 60℃, slowly add 27g of thionyl chloride to the above solution. After stirring for 6 hours, inject the reaction solution into a mixture of 250g of ice and 250g of water to obtain a precipitate. Filter the precipitate and wash the filter cake three times with 500g of ice water. Then add the filter cake to a mixed solution of 1000g of ice, 500g of water, 37g of product 1 and 15g of 3-diethylaminopropylamine. Heat the mixture to 60℃, stir for 90min, filter, and dry in an oven at 120℃ to obtain the desired synergist.

[0049] Example 1:

[0050] Take 58.13g of green pigment, 14.29g of resin (Resin), 10g of dispersant, 0.15g of synergist, and 62.56g of PMA, add 120g of 0.3mm zirconium balls, and disperse in a shaker for 10 hours. After filtration, add 80g of 0.1mm zirconium balls to the liquid and disperse in a shaker for 6 hours to obtain a dispersion. Spin-coat the dispersion onto glass, place the coated glass slide on a 120℃ heating plate and heat for 90s, then heat in an oven at 230℃ for 30 minutes. Measure the color (x, y) and contrast ratio using a contrast meter.

[0051] Example 2:

[0052] Take 58.13g of green pigment, 14.29g of resin (Resin), 10g of dispersant, 0.3g of synergist, and 62.41g of PMA, add 120g of 0.3mm zirconium balls, and disperse in a shaker for 10 hours. After filtration, add 80g of 0.1mm zirconium balls to the liquid and disperse in a shaker for 6 hours to obtain a dispersion. Spin-coat the dispersion onto glass, place the coated glass slide on a 120℃ heating plate and heat for 90s, then heat in an oven at 230℃ for 30 minutes. Measure the color (x, y) and contrast ratio using a contrast meter.

[0053] Example 3:

[0054] Take 58-12g of green pigment, 5g of resin (Resin), 4g of dispersant, 0.6g of synergist, and 2.11g of PMA. Add 120g of 0.3mm zirconium balls and disperse in a shaker for 10 hours. After filtration, add 80g of 0.1mm zirconium balls to the liquid and disperse in a shaker for 6 hours to obtain a dispersion. Spin-coat the dispersion onto glass. Place the coated glass slide on a 120℃ heating plate and heat for 90s, then heat in an oven at 230℃ for 30 minutes. Measure the color (x, y) and contrast ratio using a contrast meter.

[0055] Comparative Example 1:

[0056] Take 58.13g of green pigment, 14.29g of resin, 10g of dispersant, and 62.71g of PMA, add 120g of 0.3mm zirconium balls, and disperse in a shaker for 10 hours. After filtration, add 80g of 0.1mm zirconium balls to the liquid and disperse in a shaker for 6 hours to obtain the dispersion. Spin-coat the dispersion onto glass, place the coated glass slide on a 120℃ heating plate and heat for 90s, then heat in an oven at 230℃ for 30 minutes. Measure the color (x, y) and contrast using a contrast meter.

[0057] Comparative Example 2:

[0058] Take 58-12g of green pigment, 5g of resin (Resin), 4g of dispersant, 0.6g of product one, and 2.11g of PMA, and add 120g of 0.3mm zirconium balls. Disperse the mixture in a shaker for 10 hours. After filtration, add 80g of 0.1mm zirconium balls to the liquid and disperse it in a shaker for 6 hours to obtain the dispersion. Spin-coat the dispersion onto glass. Place the coated glass slide on a 120℃ heating plate and heat for 90s. Then heat it in an oven at 230℃ for 30 minutes and measure the color (x, y). Measure the contrast ratio using a contrast meter.

[0059] Comparative Example 3:

[0060] Take 58-12g of green pigment, 5g of resin (Resin), 4g of dispersant, 0.6g of product II, and 2.11g of PMA, and add 120g of 0.3mm zirconium balls. Disperse the mixture in a shaker for 10 hours. After filtration, add 80g of 0.1mm zirconium balls to the liquid and disperse it in a shaker for 6 hours to obtain the dispersion. Spin-coat the dispersion onto glass. Place the coated glass slide on a 120℃ heating plate and heat for 90s. Then heat it in an oven at 230℃ for 30 minutes. Measure the color (x, y) and contrast using a contrast meter.

[0061] The color pastes obtained from Examples 1-3 and Comparative Examples 1-3 were evaluated in the following experiments:

[0062] Table 1. Composition and evaluation results of green pigment paste (y = 0.50)

[0063]

[0064]

[0065] Results Analysis and Evaluation:

[0066] The synergist has a significant effect on reducing particle size and improving contrast in green pigments. The contrast will increase significantly with the increase of amount, but the amount should not be too much, otherwise it will have an adverse effect on subsequent products.

[0067] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A green pigment for colored photoresist, characterized in that, Includes the following components in parts by weight: 10 parts green pigment; 12-18 parts acrylic resin; 8-12 parts dispersant; 0.1-0.6 parts synergist; 60-70 parts propylene glycol methyl ether acetate; The structure of the synergist is shown in formula (Ⅰ):

2. The green pigment for color photoresist according to claim 1, characterized in that, The green pigment is Pigment Green G58.

3. The green pigment for color photoresist according to claim 1, characterized in that, The preparation method of the synergist includes the following steps: (1) The reaction of cyanuric chloride, p-aminobenzenesulfonic acid, and 3-diethylaminopropylamine yields product 1 with the structure of Formula 1. (2) Pigment Green G58 was reacted with 2wt% fuming sulfuric acid to give product II with the structure of formula 2; (3) The product 1 and product 2 are reacted with 3-diethylaminopropylamine to obtain an synergist with the structure of formula (I).

4. The green pigment for color photoresist according to claim 3, characterized in that, In step (1), cyanuric chloride, p-aminosulfonic acid and 3-diethylaminopropylamine are added to pure water at 15-30℃ and reacted for 0.5-1.5h. The product is then filtered, repeatedly washed and dried in an oven to obtain product one.

5. The green pigment for color photoresist according to claim 4, characterized in that, In step (1), the molar ratio of cyanuric chloride, p-aminosulfonic acid and 3-diethylaminopropylamine is 2:1:1, and the amount of pure water is 50 g / mmol cyanuric chloride.

6. The green pigment for color photoresist according to claim 3, characterized in that, In step (2), pigment green G58 and 2wt% fuming sulfuric acid solution are stirred and reacted at room temperature for 2-4 hours to obtain a reaction solution. The reaction solution is added to cold methyl ethyl ketone and stirred for 20-40 minutes to obtain a precipitate. The precipitate is then washed and filtered with methyl ethyl ketone to obtain a filter cake. The filter cake is then dried to obtain product two.

7. The green pigment for color photoresist according to claim 6, characterized in that, In step (2), the mass ratio of pigment green G58 to 2wt% fuming sulfuric acid solution is (1-2):

1.

8. The green pigment for color photoresist according to claim 3, characterized in that, In step (3), product 2 is added to N,N-dimethylformamide, and thionyl chloride is added under stirring at 50-70°C. After stirring for 5-7 hours, the reaction solution is injected into an ice-water mixture to obtain a precipitate. The precipitate is filtered and the filter cake is washed with ice water. The filter cake is added to a mixed solution of ice, water, product 1 and 3-diethylaminopropylamine. The mixture is heated to 50-70°C, stirred for 80-100 minutes, filtered and dried.

9. The green pigment for color photoresist according to claim 8, characterized in that, In step (3), the mass ratio of product 2, product 1 and 3-diethylaminopropylamine solution is 1:(3-4):(2-3).

10. The use of the green pigment for color photoresist as described in any one of claims 1-9 in the preparation of color photoresist.

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