Phthalocyanine sulfonated derivatives, process for their preparation and use thereof

Abstract

The present invention relates to the preparation of pigments, in particular to a phthalocyanine sulfonated derivative, a method for preparing the same and the use thereof as pigments for color filters. The derivative is represented by the following formula (1), and the derivative of the present invention can improve the color saturation and contrast of displays.

Description

Technical Field

[0001] This invention relates to the preparation of pigments, specifically to a phthalocyanine sulfonated derivative, its preparation method, and its application as a pigment for color filters. Background Technology

[0002] With the continuous advancement of electronic display technology, such as the rapid development of liquid crystal displays (LCDs) and organic light-emitting diode displays (OLEDs), the performance requirements for color filters are constantly increasing. Color filters are key components of color displays, their function being to achieve color image display by selecting which colors of light pass through. Therefore, high-performance pigment derivatives are needed to meet the requirements of high brightness, high contrast, and high color purity in color displays.

[0003] Meanwhile, the particle size and particle size distribution of pigments are also important indicators for evaluating pigment performance. Different particle sizes have different light scattering abilities. When the particle size is half the wavelength of light (1 / 2λ), that is, when the pigment particle diameter is 0.3-0.55um (300-550nm), the scattering ability is the strongest, which can lead to high hiding power, i.e., opacity. When the average particle size is <1 / 2λ, for example, when the particle size is 0.05-0.1um (50-100nm), it exhibits high transparency.

[0004] Existing pigments suffer from performance limitations, with issues related to particle size and dispersibility: Traditional pigments, when used in color filters, exhibit large particle sizes and poor dispersibility. Larger particle sizes negatively impact the optical performance of color filters, reducing image sharpness and color purity. To achieve high-resolution color displays, pigment derivatives require smaller particle sizes and uniform dispersion.

[0005] Existing pigments suffer from poor heat resistance and stability: During the preparation and use of color filters, they undergo high-temperature processing conditions and prolonged use, requiring pigment derivatives to possess excellent heat resistance and stability. Otherwise, the pigments may decompose, change color, or exhibit other phenomena, affecting the performance and lifespan of the color filter.

[0006] Meanwhile, traditional pigments suffer from color deviation and insufficient color gamut coverage: some pigments may deviate in color representation, failing to accurately reproduce the desired color. Moreover, to achieve broader color gamut coverage, it is necessary to develop pigment derivatives with richer color choices and superior color performance.

[0007] To address these issues, the following method is proposed for modifying color filters with pigments.

[0008] Surface treatment technology: By treating pigments to introduce specific functional groups or polymers, the dispersibility, stability, and compatibility with the filter matrix of the pigments can be improved. For example, using chemical treatment methods such as sulfonation and acylation, or adding auxiliaries such as surfactants and dispersants, can improve the performance of pigment derivatives in color filters.

[0009] Through rational molecular structure design and synthetic methods, pigment derivatives with specific properties can be prepared. For example, introducing rigid structural units or conjugated structures can improve the heat resistance, stability, and color properties of pigments.

[0010] However, with the continuous advancement of electronic display technology, the requirements for color filters are constantly increasing, and conventional pigment derivatives can no longer meet the needs.

[0011] The phthalocyanine nano pigment pastes that have been published so far do not meet the performance requirements for applications in electronic chemicals.

[0012] Toyo Ink (US5928419A) directly bonds alkyl tertiary amine groups to copper phthalocyanine molecules, effectively improving dispersibility, but its stability is poor, limiting its application. CN116265469A proposes a phthalocyanine derivative, a cyanuric chloride-bonded phthalocyanine derivative, which can achieve a particle size of 110nm, but cannot be used in electronic chemicals. Patent CN112601790A discloses adding resin during pigmentation. Through the interaction between the resin and the pigment particle growth surface, the imbalance in the particle growth direction is reduced, thereby obtaining a pigment with a small average aspect ratio, improving the contrast of the pixel area. However, the resin used will be present in the pigment, usually referred to as a pigment composition. The presence of resin in the pigment composition reduces the effective content of the pigment and decreases its color purity. Furthermore, if the resin is not chosen appropriately, the pigment may become incompatible with other components in the dispersion during later application, reducing the stability of the dispersion. In other words, the pigment composition limits the application range of the pigment. Summary of the Invention

[0013] The objective of this invention is to provide a sulfonated phthalocyanine derivative, its preparation method, and its application as a pigment in color filters.

[0014] To achieve the above objectives, the present invention adopts the following technical solution:

[0015] A sulfonated phthalocyanine derivative, the derivative being as shown in formula (1) below.

[0016]

[0017] In formula (1), each of the substituents Z1-Z16 can be the same or different and can be independently selected from H, unsubstituted or substituted by at least one of the same or different substituents; and the average number of substituents of the sulfonic acid groups Z1-Z16 is 0.1-4.

[0018] M is selected from Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, or Pb.

[0019] The substituents are metal ions or organic cations.

[0020] The metal ions are lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions, or aluminum ions; the organic cations are ethylammonium ions, butylammonium ions, dimethylammonium ions, diethylammonium ions, dialkylammonium ions, trimethylammonium ions, triethylammonium ions, trialkylammonium ions, monoethanolamine ions, diethanolammonium ions, or triethylammonium ions.

[0021] A method for preparing the phthalocyanine sulfonated derivative:

[0022] Step 1: Fuming sulfuric acid and metal phthalocyanine are heated to 0-100℃ in a closed environment and reacted for 5-10 hours. The mixture is then allowed to cool naturally to room temperature, and the crude sulfonated product is precipitated in ice water.

[0023] Step 2: After filtering and removing the filter cake, slurry it with water. After slurrying, adjust the pH to >12 with alkaline water to dissolve the sulfonation product. Filter and collect the filtrate, then acidify it with hydrochloric acid to pH <1.5. Filter and remove the filter cake, wash it with water to pH = 6-7, and dry it.

[0024] Step 3: Wash and dry repeatedly with 80% ethanol aqueous solution to remove excess impurities and obtain the derivative shown in formula (1). Determine the average sulfonation rate by solid mass spectrometry.

[0025] Step 4: The above-mentioned sulfonic acid derivatives are combined with different cations to form corresponding sulfonates.

[0026] It is obtained by sulfonation of fuming sulfuric acid containing SO3 concentration of 10-65%.

[0027] The mass ratio of fuming sulfuric acid to zinc phthalocyanine is 1-10:1; the preferred reaction temperature is 50-90℃, and the reaction time is 5-10 hours, to prepare the sulfonated product.

[0028] An application of the phthalocyanine sulfonated derivative, specifically its use as a pigment for color filters.

[0029] A pigment composition for color filters, comprising the aforementioned phthalocyanine sulfonated derivative, wherein the amount added is 3-5% by mass of the composition.

[0030] Advantages of this invention:

[0031] This invention provides sulfonated zinc phthalocyanine derivatives and their preparation methods. These derivatives, when matched with suitable resins, optimize the dispersion properties of pigment compositions for gas filter colorimeters, thereby meeting the increasing demands on color filters as electronic display technology continues to advance. Using these derivatives can improve the color saturation and contrast of displays. Detailed Implementation

[0032] The following examples further illustrate specific embodiments of the present invention. It should be noted that the specific embodiments described herein are merely for illustration and explanation and are not intended to limit the scope of the present invention.

[0033] Example 1

[0034] The synthesis steps of zinc phthalocyanine sulfonate are as follows:

[0035] In a 250ml round-bottom flask, 140g of 20% fuming sulfuric acid was added, followed by the slow addition of 20g of zinc phthalocyanine (which can be synthesized according to the literature JP2013225091 A2013-10-31) under stirring. After stirring evenly in a closed environment, the mixture was heated to 65℃ and reacted for 6 hours. After naturally cooling to room temperature, the crude sulfonated product was precipitated in a 500g ice-water mixture. After filtration, the product was dissolved in sodium hydroxide, and the pH was adjusted to >12. After filtration, the pH was adjusted to <1.5 with hydrochloric acid and acid precipitation was performed. The product was washed with water until the pH reached 6-7, dried, and then washed with 80% ethanol to obtain refined zinc phthalocyanine 18.64, with a yield of 82%. Solid-state mass spectrometry confirmed that the average sulfonation rate was around 1.0.

[0036] Example 2

[0037] The synthetic steps for barium ion sulfonated zinc phthalocyanine derivatives are as follows:

[0038] Weigh 6.91 g (0.01 mol) of the refined zinc phthalocyanine from Example 1, add it to a 500 ml round-bottom flask, add 200 g of water, dissolve 2.59 g (0.015 mol) of barium hydroxide in water, add it to the flask, heat to 60 °C and stir for 2 hours, filter, and wash continuously with 60 °C hot water to obtain 6.95 g of barium ion sulfonated derivative.

[0039] Example 3: The synthesis steps of the di-n-butylamine sulfonated zinc phthalocyanine derivative are as follows:

[0040] Weigh 6.91 g (0.01 mol) of the refined zinc phthalocyanine sulfonate from Example 1, add it to a 500 ml round-bottom flask, add 200 g of water, and add 2.61 g (0.02 mol) of di-n-butylamine while stirring. Heat to 80 °C and react for two hours. Filter and rinse with 80% ethanol aqueous solution to obtain 6.70 g of the corresponding zinc phthalocyanine sulfonate derivative.

[0041] Example 4: The synthesis steps of the (Al)-supported sulfonated derivative are as follows:

[0042] Weigh 15g of alumina and add it to 50g of ethanol and stir thoroughly. Then add it to 1000ml of water and stir evenly. Add 0.75g of the refined zinc phthalocyanine from Example 1. Adjust the pH to >12 with potassium hydroxide aqueous solution and stir at room temperature for 2 hours. Then slowly acidify with 10% hydrochloric acid to pH <3. Stir at room temperature for 1 hour, filter, wash with water, and dry to obtain 13.74g of sulfonated derivative.

[0043] Example 5: The synthesis steps of the trimethoxypropylamine sulfonated derivative are as follows:

[0044] Weigh 6.91 g (0.01 mol) of zinc phthalocyanine refined in Example 1 and add it to a 500 ml round-bottom flask. Add 200 g of water and stir until homogeneous. During stirring, slowly add 1.8 g (0.02 mol) of trimethoxypropylamine. After heating and reacting, filter and dry to obtain 6.49 g of derivative.

[0045] Example 6: The synthesis steps of the dioctadecyldimethylammonium chloride sulfonated derivative are as follows:

[0046] Weigh 6.91 g (0.01 mol) of the refined zinc phthalocyanine from Example 1 and add it to a 500 ml round-bottom flask. Add 200 g of water and stir until homogeneous. At the same time, weigh 15.64 g (0.02 ml) of dioctadecyl dimethyl ammonium chloride and dissolve it in 10 times the amount of ethanol. After dissolution, slowly add it to the homogeneous zinc phthalocyanine slurry. Heat to 60 °C and react. After washing with an ethanol-water solution and drying, obtain refined derivative 16.32.

[0047] Comparative Example 1

[0048] Add 60g of zinc halide phthalocyanine (pigment green 58), 650g of pulverized sodium chloride, 200g of diethylene glycol, and 1g of xylene to a double-arm kneader. Control the oil temperature at 120℃ and the internal temperature at 80-90℃. After kneading for 6 hours, wash the mixture to obtain the green composition G1.

[0049] Example 7

[0050] Add 60g of zinc halide phthalocyanine (pigment green 58), 650g of pulverized sodium chloride, 200g of diethylene glycol, 0.06g of refined zinc sulfonate phthalocyanine (as described in Example 1), and 1g of xylene to a double-arm kneader. Control the oil temperature at 120℃ and the internal temperature at 80-90℃. After kneading for 6 hours, wash the mixture to obtain the green composition G2.

[0051] Example 8

[0052] 60g of zinc halide phthalocyanine (pigment green 58), 650g of pulverized sodium chloride, 200g of diethylene glycol, 0.06g of refined derivative phthalocyanine from Example 2, and 1g of xylene were added to a double-arm kneader. The oil temperature was controlled at 120℃ and the internal temperature at 80-90℃. After kneading for 6 hours, the mixture was washed to obtain the green composition G3.

[0053] Example 9

[0054] Add 60g of zinc halide phthalocyanine (pigment green 58), 650g of pulverized sodium chloride, 200g of diethylene glycol, 0.06g of refined derivative phthalocyanine from Example 3, and 1g of xylene to a double-arm kneader. Control the oil temperature at 120℃ and the internal temperature at 80-90℃. After kneading for 6 hours, wash the mixture to obtain the green composition G4.

[0055] Example 10

[0056] 60g of zinc halide phthalocyanine (pigment green 58), 650g of pulverized sodium chloride, 200g of diethylene glycol, 0.06g of refined derivative phthalocyanine from Example 4, and 1g of xylene were added to a double-arm kneader. The oil temperature was controlled at 120℃ and the internal temperature at 80-90℃. After kneading for 6 hours, the mixture was washed to obtain the green composition G5.

[0057] Example 11

[0058] Add 60g of zinc halide phthalocyanine (pigment green 58), 650g of pulverized sodium chloride, 200g of diethylene glycol, 0.06g of refined derivative phthalocyanine from Example 5, and 1g of xylene to a double-arm kneader. Control the oil temperature at 120℃ and the internal temperature at 80-90℃. After kneading for 6 hours, wash the mixture to obtain the green composition G6.

[0059] Example 12

[0060] Add 60g of zinc halide phthalocyanine (pigment green 58), 650g of pulverized sodium chloride, 200g of diethylene glycol, 0.06g of refined derivative phthalocyanine from Example 6, and 1g of xylene to a double-arm kneader. Control the oil temperature at 120°C and the internal temperature at 80-90°C. After kneading for 6 hours, wash the mixture to obtain the green composition G7.

[0061] The effects of the derivatives on the particle size of the pigment compositions obtained in the above embodiments were tested using scanning electron microscopy for compositions G1-G7, with the exception of the differences in derivatives. The results are as follows (the tested particle size is the average particle size):

[0062] Pigment composition Particle size nm G1 120 G2 88 G3 60 G4 52 G5 48 G6 66 G7 52

[0063] Different pigment compositions were weighed out at 0.5g and 1g of ink thinner, respectively. After grinding, samples were scraped to obtain samples T1-T7. The effects of different derivatives on transmittance and brightness under different particle size conditions were tested.

[0064]

[0065]

[0066] As can be seen from the table above, the smaller the particle size of the composition, the greater the brightness and contrast. This indicates that the pigment composition with added pigment derivatives has a smaller and more regular particle size compared to the composition without added pigment derivatives, resulting in improved brightness and contrast. This confirms that the use of zinc sulfonated phthalocyanine derivatives can change the dispersion properties of the pigment composition, reduce the average particle size of the pigment composition, improve the uniformity of pigment ions, and enhance brightness and contrast.

Claims

1. A phthalocyanine sulfonated derivative, characterized in that: The derivative is shown in the following formula (1). In formula (1), each of the substituents Z1-Z16 can be the same or different and can be independently selected from H, unsubstituted or substituted by at least one of the same or different substituents; and the average number of substituents of the sulfonic acid groups Z1-Z16 is 0.1-4. M is selected from Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Ga, Ge, Y, Zr, Nb, In, Sn, or Pb; The substituents are metal ions or organic cations.

2. The phthalocyanine sulfonated derivative according to claim 1, characterized in that: The metal ions are lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions, or aluminum ions; the organic cations are ethylammonium ions, butylammonium ions, dimethylammonium ions, diethylammonium ions, dialkylammonium ions, trimethylammonium ions, triethylammonium ions, trialkylammonium ions, monoethanolamine ions, diethanolammonium ions, or triethylammonium ions.

3. A method for preparing the phthalocyanine sulfonated derivative of claim 1, characterized in that: Step 1: Fuming sulfuric acid and metal phthalocyanine are heated to 0-100℃ in a closed environment and reacted for 5-10 hours. The mixture is then allowed to cool naturally to room temperature, and the crude sulfonated product is precipitated in ice water. Step 2: After filtering and removing the filter cake, slurry it with water. After slurrying, adjust the pH to >12 with alkaline water to dissolve the sulfonation product. Filter and collect the filtrate, then acidify it with hydrochloric acid to pH <1.

5. Filter and remove the filter cake, wash it with water to pH = 6-7, and dry it. Step 3: Wash and dry repeatedly with 80% ethanol aqueous solution to remove excess impurities and obtain the derivative shown in formula (1). Determine the average sulfonation rate by solid mass spectrometry. Step 4: The above-mentioned sulfonic acid derivatives are combined with different cations to form corresponding sulfonates.

4. The method for preparing the phthalocyanine sulfonated derivative according to claim 3, characterized in that: It is obtained by sulfonation of fuming sulfuric acid containing SO3 concentration of 10-65%.

5. The method for preparing the phthalocyanine sulfonated derivative according to claim 3, characterized in that: The fuming sulfuric acid and zinc phthalocyanine are in a mass ratio of 1-10:1; the preferred reaction temperature is 50-90℃ and the reaction time is 5-10 hours to prepare the sulfonated product.

6. An application of the phthalocyanine sulfonated derivative according to claim 1, characterized in that: The application of the phthalocyanine sulfonated derivative as a pigment for color filters.

7. A pigment composition for a color filter, characterized in that: The composition contains the phthalocyanine sulfonated derivative of claim 1; The amount added is 3-5% of the composition mass.

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