Novel anthraquinone dye for blue photoresist color paste and synthesis method of novel anthraquinone dye

Abstract

The invention belongs to the technical field of organic dyes, and particularly provides a novel anthraquinone dye for blue photoresist color paste and a synthesis method of the novel anthraquinone dye. A synthetic method of a novel anthraquinone dye for blue photoresist color paste comprises the following steps: (1) mixing an anthraquinone derivative and a sulfonyl chlorination reagent, and carrying out sulfonyl chlorination reaction to obtain an intermediate; and (2) uniformly mixing a double-nucleophilic reaction site compound, organic alkali and a solvent, then adding the intermediate, and carrying out substitution reaction to obtain the novel anthraquinone dye for the blue photoresist color paste. The novel anthraquinone dye has excellent colored light performance, and the thermal stability, the light stability and the contrast ratio are further improved. The novel anthraquinone dye is suitable for mixed or dye blue photoresist color paste, the brightness, transparency, weather resistance and dispersity of the color paste can be remarkably improved, and in addition, the synthetic method of the novel anthraquinone dye is simple in process, low in cost and suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic dyes, and particularly relates to a novel anthraquinone dye for a blue photoresist color paste and a synthesis method thereof. BACKGROUND

[0002] In the preparation of a color photoresist color paste, the performance of a colorant plays a crucial role. Anthraquinone dyes become one of the important colorants due to excellent color saturation, light resistance and chemical stability. With the rapid development of high-resolution display devices (such as OLED and LCD), the display technology is continuously upgraded, and higher requirements are put forward for the color purity, light transmittance and process compatibility of the photoresist color paste. Due to the characteristics of the traditional pigment dispersion system, agglomeration is prone to occur, which directly affects the uniformity of the color paste and the patterning accuracy. Anthraquinone dyes can achieve high solubility and dispersion stability through molecular structure design, thereby effectively improving the performance of the color paste. At present, among the dyes used in the color photoresist color paste, azo or phthalocyanine dyes are more common, but they have obvious limitations. The light absorption characteristics of azo dyes in the short-wavelength region may interfere with the development process and affect the accuracy of development. Phthalocyanine dyes also have similar problems in short-wavelength light absorption, and the heat resistance of these two types of dyes is insufficient, which is difficult to adapt to some high-temperature process links. In contrast, anthraquinone dyes have significant advantages. Through the regulation of the conjugated structure of the anthraquinone nucleus, the absorption spectrum can be accurately regulated to match the exposure wavelength (such as g-line and i-line) of the photoresist, reducing the interference with the exposure process. At the same time, anthraquinone dyes have higher thermal stability (>200℃), which can be well adapted to high-temperature curing processes, ensuring the performance stability of the color paste after high-temperature treatment. In addition, the molecular structure design of anthraquinone dyes is flexible. By introducing polar groups such as sulfonic acid groups and amino groups, the compatibility of anthraquinone dyes with the resin system can be enhanced, the residue generated during the development process can be reduced, the development effect can be ensured, and the clarity of the pattern edge can be improved, meeting the requirements of high-resolution display devices for fine patterns. It is these characteristics that make the application value of anthraquinone dyes in the field of color photoresist color paste more prominent, providing strong support for the development of high-resolution display technology.

[0003] The patent application file with the application publication number CN104725891A discloses a preparation method of a dye. The dye prepared in this application has a structure as shown in formula (1). The dye prepared in this application does not stick and does not cake.

[0004] However, the application of anthraquinone dyes in photoresist in the prior art still faces challenges, such as insufficient thermal stability. Therefore, it is of great significance to develop new anthraquinone derivatives, optimize the molecular structure and color paste formula, so as to promote the development of high-precision color filters and micro-nano lithography technology. SUMMARY

[0005] In view of the above problems, in order to further improve the stability of the dye colorant molecules for photoresist, the application provides a new anthraquinone dye for blue photoresist color paste and a synthesis method thereof.

[0006] The application first provides a new anthraquinone dye for blue photoresist color paste, which has a structure as shown in formula A: In formula A: R 1 , R 2 Each is independently H, halogen, alkyl, aryl; X is a functional group with nucleophilicity; Y is a linking group.

[0007] Further, X is selected from the following groups: N, O, S; Y is selected from the following groups: alkyl, aryl.

[0008] Further, Y is selected from the following groups: C1-C 20 alkyl substituted or unsubstituted by halogen, C6-C 20 aryl substituted or unsubstituted by halogen, interrupted C2-C 20 linear or branched alkyl interrupted by 1 or more -O-, -CO-, -O-CO- or -CO-O-; the aryl is selected from aromatic monocyclic aromatic groups, polycyclic fused aromatic groups, and aromatic heterocyclic groups containing N, O and / or S heteroatoms.

[0009] In a second aspect, the application provides a synthesis method of a new anthraquinone dye for blue photoresist color paste, comprising the following steps: (1) mixing an anthraquinone derivative and a sulfonyl chloride reagent to perform a sulfonyl chlorination reaction to obtain an intermediate; the anthraquinone derivative has a structure as shown in IA: The intermediate has a structure as shown in IIA: (2) uniformly mixing a compound with two nucleophilic reaction sites, an organic base and a solvent, and then adding the intermediate to perform a substitution reaction to obtain a new anthraquinone dye for blue photoresist color paste.

[0010] Further, in the step (1), the sulfonyl chloridation reagent is one or both of chlorosulfonic acid and sulfuric chloride; Further, the molar ratio of the anthraquinone derivative to the sulfonyl chloridation reagent is 1:(10-50).

[0011] Further, the molar ratio of the anthraquinone derivative to the sulfonyl chloridation reagent is 1:(20-40).

[0012] Further, in the step (1), the temperature of the sulfonyl chloridation reaction is -20℃-50℃.

[0013] Further, the temperature of the sulfonyl chloridation reaction is -5℃-45℃.

[0014] Further, in the step (2), the nucleophilic group of the compound with two nucleophilic reaction sites is one or more of amino group, hydroxyl group and mercapto group. Further, the linking group of the compound with two nucleophilic reaction sites is alkyl group or aryl group. Further, the linking group of the compound with two nucleophilic reaction sites is C3-C 20 alkyl group or C6-C 20 aryl group.

[0015] Further, the nucleophilic group of the compound with two nucleophilic reaction sites is one or both of amino group and hydroxyl group. Further, the linking group of the compound with two nucleophilic reaction sites is C5-C 10 alkyl group or C5-C 10 aryl group.

[0016] Further, in the step (2), the molar ratio of the compound with two nucleophilic reaction sites to the intermediate is (1-3):1. Further, the molar ratio of the intermediate to the organic base is 1:(1-4).

[0017] Further, the molar ratio of the intermediate to the organic base is 1:(2-4).

[0018] Further, in the step (2), the organic base is one or more of triethylamine, pyridine, piperidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene and diisopropylethylamine.

[0019] Further, the organic base is one or more of triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene and diisopropylethylamine.

[0020] Further, in the step (2), the solvent is one or more of toluene, tetrahydrofuran, dichloromethane, chloroform and dichloroethane.

[0021] Further, the solvent is one or both of tetrahydrofuran and dichloromethane.

[0022] Further, in the step (2), the temperature of the substitution reaction is 0-40 DEG C.

[0023] Further, the temperature of the substitution reaction is 25-30 DEG C.

[0024] Compared with the prior art, the present application has the following beneficial effects: 1. The novel anthraquinone dye for blue photoresist color paste of the present application is constructed by reacting with a double parent nuclear reaction site compound to form an intramolecular cyclic structure, which greatly improves the weather resistance of the molecule, such as light resistance and heat resistance, so that the novel anthraquinone dye for blue photoresist color paste has higher thermal stability and light stability, and the novel anthraquinone dye for blue photoresist color paste itself has more lipid-soluble groups, thus improving the solubility and dispersibility.

[0025] 2. The novel anthraquinone dye for blue photoresist color paste provided by the present application can be mixed with other colorants to prepare a mixed or dye type photoresist color paste, which is used to improve the performance of the color paste in various aspects, such as brightness, contrast and weather resistance, and has good compatibility.

[0026] 3. The synthesis method provided by the present application has a simple route, a wide source of reagents, low cost and easy scale-up production. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 The 1H-NMR spectrum of the novel anthraquinone dye for blue photoresist color paste prepared in Example 1 of the present application is shown in the figure; Figure 2 The 1H-NMR spectrum of the novel anthraquinone dye for blue photoresist color paste prepared in Example 2 of the present application is shown in the figure; Figure 3 The 1H-NMR spectrum of the novel anthraquinone dye for blue photoresist color paste prepared in Example 3 of the present application is shown in the figure; Figure 4 The 1H-NMR spectrum of the anthraquinone dye for blue photoresist color paste prepared in Comparative Example 1 of the present application is shown in the figure. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0030] In the case of using "include", "have", and "contain" in the description herein, it is intended to cover non-exclusive inclusion, unless an explicit limiting term such as "only", "consisting of", etc. is used, and another component can be added.

[0031] The words "preferably", "more preferably", "most preferably", "particularly", "more particularly", "particularly preferably", and "most particularly preferably" in the specification describe embodiments that can provide certain benefits, under certain circumstances. However, other embodiments exist that do not provide one or more of the benefits in certain circumstances, and that may, therefore, be preferred in those circumstances. In addition, the expression of one or more preferred embodiments does not imply that other embodiments are not useful, nor does it imply that important results can only be obtained in a certain combination.

[0032] In the specification, "further", "furthermore", "in addition", and "additionally" are used to describe additional features that can be used in conjunction with other features described in the specification. However, these words do not mean that the additional features are necessary for the practice of the application.

[0033] In the specification, "at least one" means one or more, such as one, two, or more. "Multiple" or "several" means at least two, such as two, three, or more. "Multiple layers" means at least two layers, such as two, three, or more, unless otherwise explicitly specified. In the specification, "several" means at least one, such as one, two, or more, unless otherwise explicitly specified.

[0034] When a numerical range is disclosed herein, the range is to be construed as continuous, and includes the minimum and maximum values of the range, as well as every value between the minimum and maximum values. Further, when a range is provided, it is intended to include every integer within the range, unless otherwise indicated. In addition, when multiple ranges are provided, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to be inclusive of any and all sub-ranges subsumed therein.

[0035] If not otherwise specified, all steps of the present application can be performed in sequence or randomly. For example, the method comprises steps (a) and (b) means that the method can comprise steps (a) and (b) in sequence, or steps (b) and (a) in sequence. For example, the method can further comprise step (c) means that step (c) can be added to the method in any sequence, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc. Unless otherwise mentioned, the singular form of the terms can include the plural form and cannot be understood as one in number.

[0036] In the present application, "above" or "below" includes the number itself. For example, 1 below includes 1.

[0037] In the present application, room temperature refers to 0-40℃, including but not limited to 10-40℃, or further 20-30℃.

[0038] The present application is based on a large number of experimental researches, and the first aspect is to provide a novel anthraquinone dye for blue photoresist color paste, which has a structure as shown in formula A: In formula A: R 1 , R 2 Each independently is H, halogen, alkyl, aryl; X is a functional group with nucleophilicity; Y is a linking group.

[0039] In some embodiments of the present application, X is selected from the group consisting of N, O, S; and Y is selected from the group consisting of alkyl, aryl.

[0040] In some embodiments of the present application, Y is selected from the group consisting of C1-C 20 alkyl substituted or unsubstituted by halogen, C6-C 20 aryl substituted or unsubstituted by halogen, C2-C 20 linear or branched alkyl interrupted by one or more -O-, -CO-, -O-CO- or -CO-O-; and aryl selected from the group consisting of monocyclic aromatic groups, polycyclic fused aromatic groups, and aromatic heterocyclic groups containing N, O and / or S heteroatoms.

[0041] The second aspect of the present application provides a synthesis method of a novel anthraquinone dye for blue photoresist color paste, comprising the following steps: (1) taking an anthraquinone derivative and a sulfonyl chloridation reagent to mix and perform a sulfonyl chloridation reaction to obtain an intermediate; the anthraquinone derivative has a structure shown in IA: The intermediate has a structure shown in IIA: (2) taking a compound with a nucleophilic reaction site, an organic base and a solvent to mix uniformly, and then adding the intermediate to perform a substitution reaction to obtain a novel anthraquinone dye for a blue photoresist color paste.

[0042] In some embodiments of the present application, in the step (1), the sulfonyl chloridation reagent is one or both of chlorosulfonic acid and sulfoxide chloride; And / or, the molar ratio of the anthraquinone derivative to the sulfonyl chloridation reagent is 1:(10-50).

[0043] In some specific embodiments of the present application, the molar ratio of the anthraquinone derivative to the sulfonyl chloridation reagent can be 1:(10-20), 1:(20-30), 1:(30-40), 1:(40-50); typically but not limited to, for example, it can be 1:38, 1:39, 1:40, 1:41.

[0044] In some embodiments of the present application, in the step (1), the temperature of the sulfonyl chloridation reaction is -20℃-50℃.

[0045] In some specific embodiments of the present application, the temperature of the sulfonyl chloridation reaction can be -20℃-(-10)℃, -10℃-0℃, 0℃-10℃, 10℃-20℃, 20℃-30℃, 30℃-40℃, 40℃-50℃; typically but not limited to, for example, it can be 30℃, 45℃.

[0046] In some embodiments of the present application, in the step (2), the nucleophilic group of the compound with a nucleophilic reaction site is one or more of amino, hydroxyl, and mercapto; And / or, the linking group of the compound with a nucleophilic reaction site is an alkyl group or an aryl group; And / or, the linking group of the compound with a nucleophilic reaction site is a C3-C 20 alkyl group or a C6-C 20 aryl group.

[0047] In some specific embodiments of the present application, the compound with a nucleophilic reaction site can be hexanediamine, 1,6-hexanediol, 1,5-pentanediol.

[0048] In some embodiments of the present application, in the step (2), the molar ratio of the compound with a nucleophilic reaction site to the intermediate is (1-3):1. and / or, the molar ratio of the intermediate to the organic base is 1:(1.5-4).

[0049] In some embodiments of the present application, the molar ratio of the parent nucleophilic reaction site compound to the intermediate can be (1-0.5):1, (0.5-1):1, (1-1.5):1, (1.5-2):1, (2-2.5):1, (2.5-3):1; typically but not limitingly, for example, it can be 1:3.

[0050] In some embodiments of the present application, the molar ratio of the intermediate to the organic base can be 1:(1.5-2), 1:(2-2.5), 1:(2.5-3), 1:(3-3.5), 1:(3.5-4); typically but not limitingly, for example, it can be 1:3.

[0051] In some embodiments of the present application, the organic base in step (2) is one or more of triethylamine, pyridine, piperidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, diisopropylethylamine.

[0052] In some embodiments of the present application, the organic base can be one or more of triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, diisopropylethylamine; typically but not limitingly, for example, it can be triethylamine.

[0053] In some embodiments of the present application, the solvent in step (2) is one or more of toluene, tetrahydrofuran, dichloromethane, chloroform, dichloroethane.

[0054] In some embodiments of the present application, the solvent can be tetrahydrofuran.

[0055] In some embodiments of the present application, the temperature of the substitution reaction in step (2) is 0-40°C.

[0056] In some embodiments of the present application, the temperature of the substitution reaction can be 0-10°C, 10-20°C, 20-30°C, 30-40°C; typically but not limitingly, for example, it can be 20°C, 25°C, 30°C.

[0057] The present application is further illustrated by the following examples, which do not limit the scope of the present application.

[0058] When a numerical range is given in the embodiments, it should be understood that, unless otherwise specified by the present application, both ends of each numerical range and any number between the two ends can be selected. Unless otherwise defined, all technical and scientific terms used in the present application have the same meaning as commonly understood by those skilled in the art. If no specific conditions are indicated in the embodiments, the conventional conditions or the conditions recommended by the manufacturer are used. If no manufacturer of all reagents or instruments is indicated, all reagents or instruments are conventional products that can be purchased on the market. In addition to the specific methods, devices, materials used in the embodiments, any method, device and material of the prior art similar or equivalent to the methods, devices and materials described in the embodiments of the present application can also be used to implement the present application according to the mastery of the prior art by those skilled in the art and the description of the present application.

[0059] Embodiment 1 The synthesis method of the novel anthraquinone dye for blue photoresist color paste in this embodiment is as follows: (1) Take a dry and clean 1000 mL four-necked flask, place a suitable size stirring bar; add solvent blue 97 (53 g, 100 mmol, 1.0 eq.), then add chlorosulfonic acid (440 g, 3.98 mol, 40.0 eq.), stir at 45°C to 30°C for 15 min. After the temperature is maintained, start adding thionyl chloride (30 g, 252 mmol, 2.5 eq.) with a constant pressure dropping funnel, the dropping time is more than 30 min, after the dropping is completed, the reaction is carried out at room temperature overnight. Take a 5 L plastic beaker, add 3.5 L ice water mixture, slowly stir with mechanical stirring, slowly add the reaction solution into the ice water with a glass dropper, ensure that the ice does not melt during the whole process, after the dropping is completed, stir at -5°C for 30 min, filter with a Buchner funnel, wash the filter cake with ice water for 3 times, collect the filter cake, dry at 50°C, obtain 49.5 g of intermediate, the yield is 68.1%.

[0060] The chemical structural formula of the intermediate in this embodiment is shown in C1 as follows: (2) Take a dry and clean 500 mL three-necked flask, place a suitable size stirring bar; dissolve hexanediamine (9.5 g, 82 mmol, 3 eq.), triethylamine (8.3 g, 82 mmol, 3.0 eq.) in 200 mL tetrahydrofuran, add the intermediate (20 g, 27 mmol, 1.0 eq.) in multiple times under ice water bath condition (0-5°C) within 30 min, carry out the reaction at room temperature overnight. After the reaction is completed, first dilute the reaction solution with dichloromethane, then filter with a sand core funnel, finally spin dry and pass through the column to obtain 4.35 g of novel anthraquinone dye for blue photoresist color paste, the yield is 20.9%.

[0061] The chemical structural formula of the new anthraquinone dye for the blue photoresist color paste of the present embodiment is shown as follows A1: Example 2 The synthesis method of the new anthraquinone dye for the blue photoresist color paste of the present embodiment is as follows: a dry and clean 500 mL three-necked flask is taken, and a stirring bar of appropriate size is placed; 1,6-hexanediol (9.7 g, 82 mmol, 3 eq.), triethylamine (8.3 g, 82 mmol, 3.0 eq.) are dissolved in 200 mL of tetrahydrofuran, and the intermediate (20 g, 27 mmol, 1.0 eq.) is added multiple times within 30 min under ice water bath conditions (0-5°C), and the reaction is carried out at room temperature overnight. After the reaction is completed, the reaction solution is first diluted with dichloromethane, then filtered with diatomite through a sand core funnel, and finally spin-dried and columned to obtain 5.1 g of the new anthraquinone dye for the blue photoresist color paste, with a yield of 24.5%.

[0062] The chemical structural formula of the new anthraquinone dye for the blue photoresist color paste of the present embodiment is shown as follows A2: The synthesis method of the intermediate of the present embodiment is the same as that of Example 1.

[0063] Example 3 The synthesis method of the new anthraquinone dye for the blue photoresist color paste of the present embodiment is as follows: a dry and clean 500 mL three-necked flask is taken, and a stirring bar of appropriate size is placed; 1,5-pentanediol (4.3 g, 41 mmol, 3 eq.), triethylamine (4.2 g, 41 mmol, 3.0 eq.) are dissolved in 200 mL of tetrahydrofuran, and the intermediate (10 g, 14 mmol, 1.0 eq.) is added multiple times within 30 min under ice water bath conditions (0-5°C), and the reaction is carried out at room temperature overnight. After the reaction is completed, the reaction solution is first diluted with dichloromethane, then filtered with diatomite through a sand core funnel, and finally spin-dried and columned to obtain 2.7 g of the new anthraquinone dye for the blue photoresist color paste, with a yield of 25.4%.

[0064] The chemical structural formula of the new anthraquinone dye for the blue photoresist color paste of the present embodiment is shown as follows A3: The synthesis method of the intermediate of the present embodiment is the same as that of Example 1.

[0065] Comparative Example 1 The synthesis method of the anthraquinone dye for the blue photoresist color paste of the present comparative example is as follows: (1) Take a dry and clean 1000 mL four-necked flask, place a suitable size stirring bar; add solvent blue 104 (50 g, 100 mmol, 1.0 eq.), then add chlorosulfonic acid (440 g, 3.78 mol, 38 eq.), after adding, stir at 45°C to 30°C for 15 min. After the end of the incubation, start adding chlorosulfoxide (30 g, 252 mmol, 2.5 eq.) with a constant pressure dropping funnel, the dropwise addition time is more than 30 min, after the end of the dropwise addition, react overnight at room temperature. Take a 5L plastic beaker, add 3.5L ice water mixture, slowly stir with mechanical stirring, slowly add the reaction solution into the ice water with a glass dropper for quenching, ensure that the ice does not melt throughout the process, after the end of the dropwise addition, stir at -5°C for 30 min, filter with a Buchner funnel, wash the filter cake with ice water 3 times, collect the filter cake, dry at 50°C, obtain 38 g of blue intermediate C2, the yield is 56.6%.

[0066] The chemical structural formula of the intermediate of the present comparative example is shown as follows C2: (2) Take a dry and clean 500 mL three-necked flask, place a suitable size stirring bar; dissolve cyclohexylamine (8.1 g, 82 mmol, 3 eq.) and triethylamine (8.3 g, 82 mmol, 3.0 eq.) in 200 mL of tetrahydrofuran, under ice water bath conditions (0-5°C), add the intermediate (20 g, 27 mmol, 1.0 eq.) multiple times within 30 min, react overnight at room temperature. After the end of the reaction, first dilute the reaction solution with dichloromethane, then filter with a sand core funnel, finally spin dry and pass through a column to obtain 3.8 g of blue photoresist paste anthraquinone dye, the yield is 17.7%.

[0067] The chemical structural formula of the blue photoresist paste anthraquinone dye of the present comparative example is shown as follows A4: Performance test 1. Nuclear magnetic resonance hydrogen spectrum test The 1H-NMR spectrum of the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 is shown in Figures 1-3 and Figure 4 .

[0068] 2. Ultraviolet-visible absorption spectrum determination of anthraquinone dyes Prepare the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 into 10 μmol / L solution, the solvent is N,N-dimethylformamide (DMF), test the absorption spectrum in the ultraviolet-visible spectrophotometer. Calculate the molar extinction coefficient of the dye by the following formula: A = εcl In the formula, A is the light intensity; ε is the molar extinction coefficient, L / (mol·cm); c is the concentration, mol / L; and l is the thickness of the absorption layer, cm.

[0069] The results of the UV-visible absorption spectrum determination of the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 are shown in Table 1.

[0070] Table 1 Results of the UV-visible absorption spectrum determination of the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 As can be seen from Table 1, the anthraquinone dye prepared in Example 2 has a slight blue shift compared to Example 1, and has the highest molar absorption coefficient; the anthraquinone dye prepared in Example 3 has a red shift compared to Example 1, and also has a higher molar absorption coefficient.

[0071] 3. Solubility test of the anthraquinone dye The solubility of the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 in propylene glycol methyl ether acetate (PGMEA) and N,N-dimethylformamide (DMF) was tested. 10 mg of the anthraquinone dye was weighed and mixed with 100 mg of the organic solvent at room temperature for 10 min, and then left to stand for 24 h. The filtrate was filtered three times using a filter membrane, and then dried to calculate the solubility S of the anthraquinone dye: S = 100M S / M L In the formula, M S is the mass of the anthraquinone dye after drying, g; and M L is the mass of the solution, g.

[0072] The results of the solubility test of the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 are shown in Table 2.

[0073] Table 2 Results of the solubility test of the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 As can be seen from Table 2, the anthraquinone dyes prepared in Examples 1-3 have good solubility in PGMEA and DMF, and the anthraquinone dye prepared in Example 2 has the best solubility in PGMEA.

[0074] 4. Thermal stability test of the anthraquinone dye In the process of making color filter, the dye molecules should have good thermal stability at 200 DEG C or above 200 DEG C in the post-baking process. The thermal stability of anthraquinone dyes is evaluated by thermogravimetry method. The anthraquinone dyes are heated from room temperature to 500 DEG C at a heating rate of 10 DEG C / min under nitrogen protection to determine the thermal decomposition temperature T d .

[0075] The results of the thermal stability test of the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 are shown in Table 3.

[0076] Table 3 Results of the thermal stability test of the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 As shown in Table 3, the anthraquinone dyes prepared in Examples 1-3 have a T d In the range of 289-342 DEG C, the weight loss rate at 230 DEG C is less than 5%, which indicates that the above-mentioned anthraquinone dyes have good thermal stability.

[0077] The present application provides a novel anthraquinone dye for blue photoresist color paste, which can be mixed with other colorants to form a blue photoresist color paste for improving the brightness of the color paste. The anthraquinone dye has high transparency, high contrast, good dispersibility, high hiding power, coloring power and other advantages, and has good thermal stability and light stability. Meanwhile, the synthesis method is simple, low in cost and easy for large-scale production.

[0078] Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can make modifications to the technical solutions described in the foregoing embodiments, or make equivalent replacements to part of the technical features, and any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A novel anthraquinone dye for blue photoresist color paste, characterized by: Having a structure as shown in formula A: In formula A: R 1 , R 2 each independently H, halogen, alkyl, aryl; X is a functional group with nucleophilicity; Y is a linking group.

2. A novel anthraquinone dye for a blue photoresist color paste according to claim 1, characterized in that: The X is selected from the group consisting of N, O, S; the Y is selected from the group consisting of alkyl, aryl.

3. The method for synthesizing a novel anthraquinone dye for blue photoresist color paste as described in claim 1, characterized in that: Comprising the following steps: (1) Take anthraquinone derivatives and sulfuryl chloride reagent mixture, sulfuryl chlorination reaction, to obtain intermediate; the anthraquinone derivatives have the structure shown in IA: The intermediate has the structure shown in IIA: (2) The compound with two nucleophilic reaction sites, organic base, solvent mixture is uniform, then add intermediate, substitution reaction, to obtain a new anthraquinone dye for blue photoresist color paste.

4. A process for the synthesis of a novel anthraquinone dye for blue photoresist color paste according to claim 3, characterized by: In step (1), the sulfuryl chloride reagent is one or both of chlorosulfonic acid and sulfurous chloride; And / or, the molar ratio of the anthraquinone derivative to the sulfuryl chloride reagent is 1:(10-50).

5. The method for synthesizing a novel anthraquinone dye for blue photoresist pigment paste according to claim 3, characterized in that: In step (1), the temperature of the sulfuryl chlorination reaction is-20℃-50℃.

6. A novel synthesis method of anthraquinone dyes for blue photoresist color paste according to claim 3, characterized by: In step (2), the nucleophilic group of the compound with two nucleophilic reaction sites is one or several of amino, hydroxyl, and mercapto; And / or, the linking group of the compound with two nucleophilic reaction sites is alkyl or aryl; and / or the linking group of the parent nucleophilic reaction site compound is a C3-C 20 alkyl group or a C6-C 20 aryl group.

7. A novel synthesis method of anthraquinone dyes for blue photoresist color paste according to claim 3, characterized by: In step (2), the molar ratio of the compound with two nucleophilic reaction sites to the intermediate is (1-3):1; And / or, the molar ratio of the intermediate to the organic base is 1:(1-4).

8. A process for the synthesis of a novel anthraquinone dye for blue photoresist color paste according to claim 3, characterized by: In step (2), the organic base is one or several of triethylamine, pyridine, piperidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and diisopropylethylamine.

9. A novel anthraquinone dye synthesis method for a blue photoresist color paste according to claim 3, characterized by: In step (2), the solvent is one or several of toluene, tetrahydrofuran, dichloromethane, chloroform, and dichloroethane.

10. A process for the synthesis of a novel anthraquinone dye for blue photoresist color paste as claimed in claim 3, wherein the said process is characterized by: In step (2), the temperature of the substitution reaction is 0℃-40℃.

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