Pigment synergists for photoresists, compositions and methods of making and products thereof

Abstract

This invention belongs to the field of organic pigment technology, specifically relating to a pigment synergist for photoresist, a composition, its preparation method, and the product thereof. The pigment synergist for photoresist comprises the following components by weight: 42 parts of Acid Yellow 42, 5-10 parts of Thionyl Chloride, and 6-8 parts of 3-Diethylaminopropylamine. The invention also provides a preparation method for the pigment synergist, a pigment composition containing the pigment synergist, a method for preparing the pigment composition, a kneading method for the pigment composition, a modified pigment obtained by kneading, a color paste composition containing the modified pigment, and a method for preparing the color paste composition. Compared to existing technologies, the pigment synergist for photoresist can effectively improve the dispersion of pigments in color pastes and enhance the contrast of the color paste.

Description

Technical Field

[0001] This invention relates to a pigment synergist for photoresists, its composition, preparation method, and product, belonging to the field of organic pigment technology. Background Technology

[0002] Pigment Red 254 (R254) is a high-performance red organic pigment with advantages such as pure color, good weather resistance, and heat stability. It is widely used in liquid crystal filters, high-end inks, coatings, and plastic coloring. However, this pigment has high surface polarity and its particles are prone to agglomeration, making it difficult to disperse in application systems. It usually requires a large amount of dispersant to achieve stable dispersion. The addition of dispersant alone cannot continuously improve contrast and increases costs while deteriorating system stability.

[0003] Existing technologies mostly employ simple salt milling, simple resin coating, or ordinary dispersant treatment, which have drawbacks such as limited dispersion effect, insignificant contrast improvement, and large amount of dispersant used, making it difficult to meet the requirements of high-end display fields for high contrast and high dispersion.

[0004] Therefore, developing a pigment red 254 color paste formulation technology with low dispersant addition, high contrast, uniform particle dispersion, and strong stability is a technical problem that those skilled in the art expect to solve. Summary of the Invention

[0005] This invention addresses the technical problems of limited pigment dispersion, insignificant contrast enhancement, and large dispersant dosage in existing technologies by providing a pigment synergist for photoresists, a composition, and its preparation method and product.

[0006] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: A pigment enhancer for photoresist, comprising the following components in parts by weight: 42 parts of CIAcid Yellow 42, 5-10 parts of thionyl chloride, and 6-8 parts of 3-diethylaminopropylamine.

[0007] The present invention also provides a method for preparing the pigment synergist for photoresist, comprising the following steps: (1) Mix N,N-dimethylformamide and Acid Yellow 42, add thionyl chloride to react, and separate to obtain the intermediate precipitate; (2) The intermediate precipitate obtained in step (1) is mixed with 3-diethylaminopropylamine dispersion and separated to obtain the pigment enhancer for photoresist.

[0008] Preferably, the mass amount of N,N-dimethylformamide is 98-102 parts.

[0009] Preferably, the mixing method in step (1) is stirring, and the stirring speed is 150-200 rpm.

[0010] Preferably, the addition of thionyl chloride in step (1) is done by dripping.

[0011] Preferably, the reaction in step (1) is carried out at a temperature of 30-40°C for 3-6 hours.

[0012] More preferably, an ice-water mixture is added after the reaction time in step (1) has elapsed.

[0013] More preferably, the mass of the ice-water mixture is 500 parts.

[0014] Most preferably, the mass ratio of ice to water in the ice-water mixture is 1:1.

[0015] Preferably, the separation method in step (1) is negative pressure filtration.

[0016] Preferably, the 3-diethylaminopropylamine dispersion in step (2) is prepared by mixing the formulated amount of 3-diethylaminopropylamine with 300 parts by mass of deionized water.

[0017] Preferably, the mixing method in step (2) is stirring, and the stirring time is 2.5-3.5h.

[0018] Preferably, the separation method in step (2) is negative pressure filtration.

[0019] Preferably, step (2) includes a washing step after the separation step.

[0020] More preferably, the washing method is to wash with deionized water until pH=7.

[0021] Most preferably, the washed product is dried to constant weight at a temperature of 60-80°C.

[0022] The present invention also provides a pigment composition containing the above-mentioned pigment synergist for photoresists, comprising the following raw material components: Pigment Red 254, pigment synergist for acrylic resins and photoresists; The acrylic resin is obtained by free radical polymerization of benzyl methacrylate and methacrylic acid. The molar ratio of benzyl methacrylate to methacrylic acid is 68-72:28-32.

[0023] Preferably, the molar ratio of benzyl methacrylate to methacrylic acid is 70:30.

[0024] Preferably, the reaction temperature for the free radical polymerization is 70-90°C.

[0025] Preferably, the reaction time for the free radical polymerization is 4-8 hours.

[0026] Preferably, the product separation method of the free radical polymerization is the anti-solvent method.

[0027] Preferably, the acrylic resin has a weight-average molecular weight of 12,000, an acid value of 115 mgKOH / g, and a solid content of 28-30%.

[0028] Preferably, the amount of pigment synergist used in the photoresist is 2-10% of Pigment Red 254.

[0029] More preferably, the amount of pigment synergist used in the photoresist is 5% of Pigment Red 254.

[0030] Preferably, the mass amount of the acrylic resin is 5-20% of Pigment Red 254.

[0031] More preferably, the mass of the acrylic resin is 10% of Pigment Red 254.

[0032] The present invention also provides a kneading method using the above-described pigment composition, comprising the following steps: Pigment Red 254, sodium chloride, acrylic resin, and photoresist are heated, kneaded, washed, separated, and dried using a pigment synergist to obtain the kneaded modified pigment.

[0033] Preferably, the amount of sodium chloride used is 8-10 times that of Pigment Red 254.

[0034] More preferably, the amount of sodium chloride used is 8 times that of Pigment Red 254.

[0035] Preferably, the heating and kneading temperature is 78-82℃ and the time is 11.5-12.5h.

[0036] More preferably, the heating and kneading temperature is 80°C and the time is 12 hours.

[0037] Preferably, the washing method involves pulping and filtering with water at 80-90°C until the filtrate is free of chloride ions.

[0038] Preferably, the separation of products is carried out by negative pressure filtration.

[0039] Preferably, the drying temperature is 70-90℃ and the time is 8-12h.

[0040] More preferably, the drying endpoint is a moisture content of less than 1%.

[0041] Preferably, the kneading method further includes the step of pulverizing the product through a 200-400 mesh sieve.

[0042] The present invention also provides modified pigments obtained by the above kneading method.

[0043] The present invention also provides a color paste composition containing the above-described modified pigment, comprising the following raw material components in parts by weight: 12 parts modified pigment, 5 parts acrylic resin, 0.15-0.6 parts pigment synergist for photoresist and 3.5-7 parts dispersant.

[0044] The present invention also provides a method for preparing the above-mentioned color paste composition, comprising the following steps: The mixture of modified pigments, acrylic resin, pigment synergist for photoresist, dispersant and solvent is subjected to primary grinding followed by secondary grinding.

[0045] Preferably, the primary grinding is performed using 0.3mm zirconium balls.

[0046] Preferably, the secondary grinding is performed using 0.1mm zirconium balls.

[0047] Preferably, the dispersant is BYK Chemical wetting and dispersing agent DISPERBYK-2001.

[0048] The beneficial effects of this invention are as follows: The pigment synergist of this invention is prepared by grafting acid yellow 42 with acyl chloride. It has both aromatic groups that strongly adsorb pigments and long-chain alkyl solvation segments, which can anchor the surface of pigment particles and inhibit agglomeration through steric hindrance and electrostatic repulsion. When combined with acrylic resin to modify the pigment in situ during the kneading stage, the surface properties of the pigment are optimized, and its dispersion uniformity in the photoresist system is significantly improved, thus improving the defect of poor pigment dispersion. This invention utilizes the synergistic effect of pigment synergists and acrylic resins in a specific ratio, combined with a high-temperature kneading process to refine the primary particle size and narrow the particle size distribution of Pigment Red 254, thereby reducing the light scattering loss of the pigment paste. At the same time, the structure of the synergist matches the optical properties of Pigment Red 254, which can enhance color saturation and optical contrast, significantly improve the display quality of the photoresist of the filter, and make up for the problem of insufficient contrast improvement in the prior art. Attached Figure Description

[0049] Figure 1 The reaction equation diagram of the pigment synergist for photoresist provided by the present invention; Figure 2 This is a particle size characterization diagram of the pigment composition obtained in Example 7 of the present invention; Figure 3 This is a mass spectrum of the pigment synergist for photoresist obtained in Example 1 of the present invention. Detailed Implementation

[0050] The principles and features of the present invention are described below with reference to embodiments. The embodiments are only used to explain the present invention and are not intended to limit the scope of the present invention.

[0051] For the sake of simplicity, unless otherwise specified, the "parts" mentioned in the specific embodiments of the present invention refer to parts by mass.

[0052] Unless otherwise specified, all raw materials used in this invention are commercially available products.

[0053] The acrylic resin used in this invention is obtained by conventional copolymerization of benzyl methacrylate and methacrylic acid as polymeric monomers, wherein the molar ratio of benzyl methacrylate to methacrylic acid is 70:30; the specific parameters are: weight average molecular weight Mw=12000; acid value=115mgKOH / g; solid content NV=29%.

[0054] Example 1: A pigment synergist for photoresist and its preparation method (1) Add 100 parts of N,N-dimethylformamide to a dry reaction vessel, start stirring, control the speed at 200 r / min, slowly add 42 parts of Acid Yellow 42, stir until completely dispersed and uniform, then slowly add 7 parts of thionyl chloride under the condition of ice-water bath temperature control at 5℃, keep the temperature at 40℃ for 5h, pour the reaction mixture into ice water obtained by mixing 250 parts of ice and 250 parts of water, quickly quench to terminate the reaction, precipitate a single-sided monosubstituted structure, and obtain a single-sided monochlorosulfonyl filter cake by negative pressure filtration; (2) Add the filter cake to 300 parts of water and 7 parts of 3-diethylaminopropylamine, stir for 3 hours, filter under reduced pressure, collect the filter cake, wash it with deionized water, wash the filter cake with distilled water until the pH of the filtrate is 7, dry the filter cake at 70°C to constant weight, and obtain the pigment enhancer for photoresist. according to Figure 3 It can be seen that the theoretical molecular weight of the pigment synergist for photoresist obtained in this embodiment is 848.25, and the actual measured molecular weight is 825.16 (M-Na).

[0055] Example 2: A pigment synergist for photoresist and its preparation method (1) Add 100 parts of N,N-dimethylformamide to a dry reaction vessel, start stirring, control the speed at 150 r / min, slowly add 42 parts of acid yellow 42, stir until completely dispersed and uniform, then slowly add 6 parts of thionyl chloride under controlled temperature of 5℃, keep the temperature at 30℃ for 5h, pour the reaction mixture into ice water obtained by mixing 250 parts of ice and 250 parts of water, quickly quench to terminate the reaction, precipitate a single-sided monosubstituted structure, and obtain a single-sided monochlorosulfonyl filter cake by negative pressure filtration; (2) Add the filter cake to 300 parts of water and 6 parts of 3-diethylaminopropylamine, stir for 3 hours, filter under reduced pressure, collect the filter cake, wash it with deionized water, wash the filter cake with distilled water until the pH of the filtrate is 7, dry the filter cake at 70°C to constant weight, and obtain the pigment enhancer for photoresist.

[0056] Example 3: A pigment synergist for photoresist and its preparation method (1) Add 100 parts of N,N-dimethylformamide to a dry reaction vessel, start stirring, control the speed at 180 r / min, slowly add 42 parts of Acid Yellow 42, stir until completely dispersed and uniform, then slowly add 10 parts of thionyl chloride at 5℃, keep the temperature at 40℃ for 3h, pour the mixture after reaction into ice water obtained by mixing 250 parts of ice and 250 parts of water, quickly quench to terminate the reaction, precipitate a single-sided monosubstituted structure, and obtain a single-sided monochlorosulfonyl filter cake by negative pressure filtration; (2) Add the filter cake to 300 parts of water and 8 parts of 3-diethylaminopropylamine, stir for 3 hours, filter under reduced pressure, collect the filter cake, wash it with deionized water, wash the filter cake with distilled water until the pH of the filtrate is 7, dry the filter cake at 70°C to constant weight, and obtain the pigment enhancer for photoresist.

[0057] Example 4: A pigment composition and its preparation method Take 100 parts of Pigment Red 254, 5 parts of the pigment synergist for photoresist obtained in Example 1, 800 parts of sodium chloride, and 10 parts of acrylic resin, premix them, put them into a kneader, seal it, and start heating. Heat the mixture to 80°C and knead it at a constant temperature for 12 hours. After kneading, take out the material, add 80°C deionized water, stir and slurry it to completely dissolve the sodium chloride. Then, perform vacuum filtration, and wash the filter cake repeatedly with hot water until no chloride ions are detected in the filtrate (no white precipitate is detected by silver nitrate). After filtration, drying, and washing, the filter cake is filtered under reduced pressure to remove free water. It is then placed in a vacuum drying oven and dried at 70°C until the moisture content is less than 1%. The dried block material is then mechanically crushed and passed through a 200-mesh sieve to obtain Red 254 K-1, a highly dispersed and high-contrast modified pigment.

[0058] Example 5: A pigment composition and its preparation method Take 100 parts of Pigment Red 254, 5 parts of the pigment synergist for photoresist obtained in Example 2, 800 parts of sodium chloride, and 10 parts of acrylic resin, premix them, put them into a kneader, seal it, and start heating. Heat the mixture to 80°C and knead it at a constant temperature for 12 hours. After kneading, take out the material, add 80°C deionized water, stir and slurry it to completely dissolve the sodium chloride. Then, perform vacuum filtration, and wash the filter cake repeatedly with hot water until no chloride ions are detected in the filtrate (no white precipitate is detected by silver nitrate). After filtration, drying, and washing, the filter cake is filtered under reduced pressure to remove free water. It is then placed in a vacuum drying oven and dried at 70°C until the moisture content is less than 1%. The dried blocky material is then mechanically crushed and passed through a 200-mesh sieve to obtain highly dispersed, high-contrast modified pigment Red 254 K-2.

[0059] Example 6: A pigment composition and its preparation method Take 100 parts of Pigment Red 254, 5 parts of the pigment synergist for photoresist obtained in Example 3, 800 parts of sodium chloride, and 10 parts of acrylic resin, premix them, put them into a kneader, seal it, and start heating. Heat the mixture to 80°C and knead it at a constant temperature for 12 hours. After kneading, take out the material, add 80°C deionized water, stir and slurry it to completely dissolve the sodium chloride. Then, perform vacuum filtration, and wash the filter cake repeatedly with hot water until no chloride ions are detected in the filtrate (no white precipitate is detected by silver nitrate). After filtration, drying, and washing, the filter cake is filtered under reduced pressure to remove free water. It is then placed in a vacuum drying oven and dried at 70°C until the moisture content is less than 1%. The dried blocky material is then mechanically crushed and passed through a 200-mesh sieve to obtain highly dispersed, high-contrast modified pigment Red 254 K-3.

[0060] Example 7 A color paste composition and its preparation method Add 12g Red 254 K-1, 5g acrylic resin, 3.5g DISPERBYK-2001 dispersant, 0.6g pigment enhancer for photoresist obtained in Example 1, and 78.9g solvent propylene glycol methyl ether acetate to a glass container. Add 120g of 0.3mm zirconium balls. Place the glass container containing the above materials in a shaker and disperse for 10 hours. After filtration, add 60g of 0.1mm zirconium balls to the filtrate and continue to disperse in a shaker for 8 hours to obtain a dispersed color paste.

[0061] Example 8 A color paste composition and its preparation method Add 12g Red 254 K-1, 5g acrylic resin, 4g DISPERBYK-2001 dispersant, 0.6g pigment enhancer for photoresist obtained in Example 1, and 78.4g solvent propylene glycol methyl ether acetate to a glass container. Add 120g of 0.3mm zirconium balls. Place the glass container containing the above materials in a shaker and disperse for 10 hours. After filtration, add 60g of 0.1mm zirconium balls to the filtrate and continue to disperse in a shaker for 8 hours to obtain a dispersed color paste.

[0062] Example 9 A color paste composition and its preparation method Add 12g Red 254 K-1, 5g acrylic resin, 4g DISPERBYK-2001 dispersant, 0.3g pigment enhancer for photoresist obtained in Example 1, and 78.7g solvent propylene glycol methyl ether acetate to a glass container. Add 120g of 0.3mm zirconium balls. Place the glass container containing the above materials in a shaker and disperse for 10 hours. After filtration, add 60g of 0.1mm zirconium balls to the filtrate and continue to disperse in a shaker for 8 hours to obtain a dispersed color paste.

[0063] Example 10 A color paste composition and its preparation method Add 12g Red 254 K-1, 5g acrylic resin, 5g DISPERBYK-2001 dispersant, 0.2g pigment enhancer for photoresist obtained in Example 1, and 77.8g solvent propylene glycol methyl ether acetate to a glass container. Add 120g of 0.3mm zirconium balls. Place the glass container containing the above materials in a shaker and disperse for 10 hours. After filtration, add 60g of 0.1mm zirconium balls to the filtrate and continue to disperse in a shaker for 8 hours to obtain a dispersed color paste.

[0064] Example 11 A color paste composition and its preparation method Add 12g Red 254 K-1, 5g acrylic resin, 5g DISPERBYK-2001 dispersant, 0.15g pigment synergist for photoresist obtained in Example 1, and 77.85g solvent propylene glycol methyl ether acetate to a glass container. Add 120g of 0.3mm zirconium balls. Place the glass container containing the above materials in a shaker and disperse for 10 hours. After filtration, add 60g of 0.1mm zirconium balls to the filtrate and continue to disperse in a shaker for 8 hours to obtain a dispersed color paste.

[0065] Example 12 A color paste composition and its preparation method Add 12g Red 254 K-2, 5g acrylic resin, 3.5g DISPERBYK-2001 dispersant, 0.6g pigment synergist for photoresist obtained in Example 2, and 78.9g solvent propylene glycol methyl ether acetate to a glass container. Add 120g of 0.3mm zirconium balls. Place the glass container containing the above materials in a shaker and disperse for 10 hours. After filtration, add 60g of 0.1mm zirconium balls to the filtrate and continue to disperse in a shaker for 8 hours to obtain a dispersed color paste.

[0066] Example 13 A color paste composition and its preparation method Add 12g Red 254 K-3, 5g acrylic resin, 3.5g DISPERBYK-2001 dispersant, 0.6g pigment enhancer for photoresist obtained in Example 3, and 78.9g solvent propylene glycol methyl ether acetate to a glass container. Add 120g of 0.3mm zirconium balls. Place the glass container containing the above materials in a shaker and disperse for 10 hours. After filtration, add 60g of 0.1mm zirconium balls to the filtrate and continue to disperse in a shaker for 8 hours to obtain a dispersed color paste.

[0067] Comparative Example 1 Add 12g Red 254 K-1, 5g acrylic resin, 5g DISPERBYK-2001 dispersant, and 78g solvent propylene glycol methyl ether acetate to a glass container. Add 120g of 0.3mm zirconium balls. Place the glass container containing the above materials into a shaker and disperse for 10 hours. After filtration, add 60g of 0.1mm zirconium balls to the liquid and disperse in a shaker for 8 hours to obtain a dispersed color paste.

[0068] Comparative Example 2 Add 12g Red 254 K-1, 5g acrylic resin, 7g DISPERBYK-2001 dispersant, and 76g solvent propylene glycol methyl ether acetate to a glass container. Add 120g of 0.3mm zirconium balls. Place the glass container containing the above materials into a shaker and disperse for 10 hours. After filtration, add 60g of 0.1mm zirconium balls to the liquid and disperse in a shaker for 8 hours to obtain a dispersed color paste.

[0069] Comparative Example 3 12g R254, 5g acrylic resin, 3.5g DISPERBYK-2001 dispersant, 78.9g solvent propylene glycol methyl ether acetate, and 0.6g pigment enhancer for photoresist obtained in Example 1 were added to a glass container. 120g of 0.3mm zirconium balls were added, and the glass container containing the above materials was placed in a shaker and dispersed for 10 hours. After filtration, 60g of 0.1mm zirconium balls were added to the liquid, and the mixture was placed in a shaker and dispersed for 8 hours to obtain a dispersed color paste.

[0070] Test case The dispersed pigments obtained in Examples 7-13 and Comparative Examples 1-3 were spin-coated onto glass. The coated glass slides were placed on a 120°C heating plate and heated for 90 seconds, then heated in an oven at 230°C for 30 minutes. The colorimetric values ​​(x, y) were measured, and the contrast ratio was measured using a contrast meter.

[0071] The particle size characterization method in Example 7 was performed using a Brookhaven 90Plus Pals particle size analyzer, with the test sample diluted 2000 times.

[0072] The components, dosages, and contrast ratios of the dispersed pigments in the above embodiments and comparative examples are shown in the table below: Table 1. Comparison of components and performance data of dispersible pigments in the examples and comparative examples.

[0073] As can be seen from the table above, Embodiments 7-11 provided by the present invention all exhibit high contrast advantages, with contrast ratios all exceeding 5600, which is far higher than the maximum value of 4500 of Comparative Examples 1-3. Comparative Example 1 is a blank control without the addition of synergist and using the conventional amount of dispersant. The absence of synergist in it resulted in a significant decrease in contrast, indicating that the synergist is a functional component of the products provided by this invention. Comparative Example 2 is a control group that uses an alternative solution without adding a synergist but with a significantly increased amount of commercially available dispersant. This clearly demonstrates that simply increasing the amount of dispersant cannot achieve the effects of this invention. Figure 2 The good particle fineness exhibited in Example 7 indicates that the synergist has a synergistic effect in improving contrast and dispersion; Comparative Example 3 was a control group with the addition of a synergist, where only the modified raw material of the present invention was replaced with ordinary unbranded R254 pigment. This demonstrates that the contrast performance of the Red 254 K-1 modified pigment provided by the present invention is far superior to that of ordinary R254.

[0074] 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 pigment synergist for photoresist, characterized in that, The raw materials include the following components by weight: Acid Yellow 42 parts, thionyl chloride 5-10 parts, 3-diethylaminopropylamine 6-8 parts.

2. The method for preparing the pigment synergist for photoresist according to claim 1, characterized in that, Includes the following steps: (1) Mix N,N-dimethylformamide and Acid Yellow 42, add thionyl chloride to react, and separate to obtain the intermediate precipitate; (2) The intermediate precipitate obtained in step (1) is mixed with 3-diethylaminopropylamine dispersion and separated to obtain the pigment enhancer for photoresist.

3. The preparation method according to claim 2, characterized in that, The mass amount of N,N-dimethylformamide used is 98-102 parts.

4. A pigment composition containing the pigment synergist for photoresist according to claim 1, characterized in that, Includes the following raw material components: Pigment Red 254, pigment synergist for acrylic resins and photoresists; The acrylic resin is obtained by free radical polymerization of benzyl methacrylate and methacrylic acid. The molar ratio of benzyl methacrylate to methacrylic acid is 68-72:28-32.

5. The pigment composition according to claim 4, characterized in that, The amount of pigment synergist used in the photoresist is 2-10% of Pigment Red 254.

6. The pigment composition according to claim 4, characterized in that, The mass of the acrylic resin used is 5-20% of Pigment Red 254.

7. The kneading method of the pigment composition according to any one of claims 4-6, characterized in that, Includes the following steps: Pigment Red 254, sodium chloride, acrylic resin, and photoresist are heated, kneaded, washed, separated, and dried using a pigment synergist to obtain the kneaded modified pigment.

8. The modified pigment obtained by the kneading method according to claim 7.

9. A color paste composition containing the modified pigment of claim 8.

10. The method for preparing the color paste composition according to claim 9, characterized in that, Includes the following steps: The mixture of modified pigments, acrylic resin, pigment synergist for photoresist, dispersant and solvent is subjected to primary grinding followed by secondary grinding.

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