Phthalocyanine sulfonamide derivative dye as well as preparation method and application thereof

Abstract

The invention provides a phthalocyanine sulfonamide derivative dye as well as a preparation method and application thereof, and belongs to the technical field of phthalocyanine series dyes. The structural general formula of the phthalocyanine sulfonamide derivative dye is (PC)-(SO2-N-X) z-(SO3R) y, PC is a phthalocyanine or metal phthalocyanine group, X is hydrogen, C1-C14 alkyl, hydroxyalkyl, aralkyl or aromatic group, R is hydrogen, C1-C4 alkyl or amine salt cation, the value range of z is 1-4, the value range of y is 1-3, and the sum of z and y is less than or equal to 4. According to the invention, the sulfonamide group and the sulfonic acid group are introduced at the same time, so that the prepared derivative dye has excellent organic solvent solubility and water solubility, and the problem of single solubility of the traditional zinc phthalocyanine dye is effectively solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of phthalocyanine series dyes, in particular to a phthalocyanine sulfonamide derivative dye and a preparation method and application thereof. BACKGROUND

[0002] As an important dye and pigment, zinc phthalocyanine compounds are widely used in the production of electronic chemicals such as display panels due to their excellent light fastness, color stability and chemical stability. However, traditional zinc phthalocyanine dyes have the problems of limited solubility and single application scenario: some zinc phthalocyanine sulfonic acid derivatives are only suitable for aqueous systems, and zinc phthalocyanine compounds without substituents have low solubility in organic solvents, which cannot meet the diversified application requirements.

[0003] In the prior art, although attempts have been made to improve water solubility by introducing sulfonic acid groups or to prepare sulfonamide derivatives through amination reaction, the obtained products have the problems of single function, complex preparation process and low yield. For example, although some sulfonamide-substituted phthalocyanine dyes improve the solubility in organic solvents, they sacrifice the developing ability for display panels; and although multi-sulfonic acid group phthalocyanines have excellent water solubility, they have poor dispersibility in organic media, which seriously limits their application in the field of electronic chemicals and the like.

[0004] Therefore, it is of great significance to provide a phthalocyanine sulfonamide derivative dye which has diversified solubility, excellent application performance and simple preparation process. SUMMARY

[0005] In order to solve the above technical problems, the purpose of the present application is to provide a phthalocyanine sulfonamide derivative dye and a preparation method and application thereof.

[0006] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions: The present application provides a phthalocyanine sulfonamide derivative dye, and the structural general formula of the phthalocyanine sulfonamide derivative dye is (PC)-(SO2-N-X) z -(SO3R) y , wherein PC is a phthalocyanine or metal phthalocyanine group, X is hydrogen, C1-C14 alkyl, hydroxyalkyl, aralkyl or aromatic group, R is hydrogen, C1-C4 alkyl or amine salt cation, the value range of z is 1-4, the value range of y is 1-3, and z+y≤4.

[0007] Further, when the PC is a metal phthalocyanine group, the metal includes copper, zinc, nickel or cobalt.

[0008] The present application provides a preparation method of the phthalocyanine sulfonamide derivative dye, comprising the following steps: 1) reacting phthalocyanine, chlorosulfonic acid and thionyl chloride to obtain phthalocyanine sulfuryl chloride; 2) performing amination reaction of phthalocyanine sulfuryl chloride and amine compound in a solvent to obtain phthalocyanine sulfamide derivative dye.

[0009] Further, the mass ratio of the phthalocyanine, chlorosulfonic acid and thionyl chloride is 40-65:160-220:75-105; The mass ratio of the phthalocyanine sulfuryl chloride, amine compound and solvent is 5-15:35-55:100-1200.

[0010] Further, in the step 1), the phthalocyanine is phthalocyanine or metal phthalocyanine; The temperature of the reaction is 90-138℃, and the reaction time is 3-8h.

[0011] Further, in the step 2), the amine compound includes one or more of propanol-1,3-diamine, 3-(2'-ethylhexyloxy)-propyl-1-amine, dodecylamine and aniline; The solvent includes one or more of water, ethanol, pyridine and nitrobenzene; The temperature of the amination reaction is 20-60℃, the amination reaction time is 1-12h, and the pH of the amination reaction is 5.6-9.6.

[0012] The application provides a preparation method of the phthalocyanine sulfamide derivative dye.

[0013] Further, the benzene derivative containing sulfamide group includes phthalic acid-4-sulfamide and / or 1,2-dibromobenzene-4-sulfobenzamide; The metal salt includes zinc chloride; The catalyst includes boric acid and / or ammonium molybdate; The mass ratio of the benzene derivative containing sulfamide group, urea, metal salt and catalyst is 80-120:250-350:20-30:2-6.

[0014] Further, the temperature of the ring closure reaction is 150-210℃, and the ring closure reaction time is 8-10h.

[0015] The application also provides application of the phthalocyanine sulfamide derivative dye in photoresist or display panel pigment.

[0016] The application has the following beneficial effects: 1) The prepared derivative dye has excellent organic solvent solubility and water solubility by simultaneously introducing sulfonamide groups and sulfonic acid groups, effectively solving the problem of single solubility of traditional zinc phthalocyanine dyes; in the application of photoresist, the derivative can significantly reduce the particle size of the dispersion, improve the uniformity and stability of the system, thereby overcoming the technical problem of easy agglomeration of traditional multi-sulfonic acid group products in organic media; 2) While realizing the breakthrough of solubility and application performance, the derivative dye prepared in the present application inherits the inherent excellent performance of phthalocyanine dyes, such as high light fastness, good chemical stability and color stability; as an additive of photoresist pigment, it can significantly improve the brightness, improve the color performance, and promote the formation of regular porous structure, which is beneficial to development and patterning, not only overcoming the problem of lack of development ability of some existing sulfonamide derivatives, but also meeting the strict requirements of precise pattern forming in display panel manufacturing; 3) The present application provides two main synthesis paths of phthalocyanine sulfonamide chloroamination method and closed ring method containing sulfonamide precursor, the process is flexible and variable, and can be selected according to the structure of the target product, which is easy to operate and helps to realize high yield and controllable substitution degree. DETAILED DESCRIPTION

[0017] The present application provides a phthalocyanine sulfonamide derivative dye, the structure general formula of the phthalocyanine sulfonamide derivative dye is: (PC)-(SO2-N-X) z -(SO3R) y , Wherein, PC is a phthalocyanine or metal phthalocyanine group, X is hydrogen, C1-C14 alkyl, hydroxyalkyl, aralkyl or aromatic group, R is hydrogen, C1-C4 alkyl or amine salt cation, the value range of z is 1-4, the value range of y is 1-3, and z+y≤4.

[0018] Preferably, PC is a metal phthalocyanine group, X is hydrogen, C2-C10 alkyl, hydroxyalkyl, aralkyl or aromatic group, R is hydrogen, C2-C4 alkyl or amine salt cation, the value range of z is 1-3, the value range of y is 1-2, and z+y≤4.

[0019] Further preferably, PC is a phthalocyanine or metal phthalocyanine group, X is hydrogen, C3-C6 alkyl, hydroxyalkyl, aralkyl or aromatic group, R is hydrogen, C2-C3 alkyl, alkyl amine salt, ethanol amine salt, the value range of z is 2-3, the value range of y is 2, and z+y≤4.

[0020] In the present application, when the PC is a metal phthalocyanine group, the metal includes copper, zinc, nickel or cobalt, preferably copper, zinc or nickel, and further preferably zinc.

[0021] The application provides a preparation method of the phthalocyanine sulfonamide derivative dye. 1) reacting phthalocyanine, chlorosulfonic acid and thionyl chloride to obtain phthalocyanine sulfonyl chloride; 2) performing amination reaction on the phthalocyanine sulfonyl chloride and an amine compound in a solvent to obtain the phthalocyanine sulfonamide derivative dye.

[0022] In the application, the mass ratio of the phthalocyanine, the chlorosulfonic acid and the thionyl chloride is 40-65:160-220:75-105, preferably 43-62:162-210:77-101, and more preferably 46-57.5:164-205:78.4-98; The mass ratio of the phthalocyanine sulfonyl chloride, the amine compound and the solvent is 5-15:35-55:100-1200, preferably 7-13:38-52:300-1100, and more preferably 10:40-50:500-1000.

[0023] In the step 1) of the application, the phthalocyanine is phthalocyanine or metal phthalocyanine, preferably metal phthalocyanine, and more preferably zinc phthalocyanine.

[0024] In the step 1) of the application, the reaction temperature is 90-138℃, preferably 95-137℃, and more preferably 100-136℃; and the reaction time is 3-8h, preferably 4-7h, and more preferably 5-6h.

[0025] In the step 2) of the application, the amine compound includes one or more of propan-1,3-diamine, 3-(2'-ethylhexyloxy)-propyl-1-amine, dodecylamine and aniline, preferably one or more of propan-1,3-diamine, 3-(2'-ethylhexyloxy)-propyl-1-amine and dodecylamine, and more preferably 3-(2'-ethylhexyloxy)-propyl-1-amine and / or dodecylamine.

[0026] In the step 2) of the application, the solvent includes one or more of water, ethanol, pyridine and nitrobenzene, preferably one or more of water, ethanol and nitrobenzene, and more preferably water and / or ethanol.

[0027] In the step 2) of the application, the temperature of the amination reaction is 20-60℃, preferably 30-60℃, and more preferably 40-60℃; the time of the amination reaction is 1-12h, preferably 2-10h, and more preferably 3-8h; and the pH of the amination reaction is 5.6-9.6, preferably 5.8-9.4, and more preferably 6.0-9.2.

[0028] In the present application, after the amination reaction is completed, post-treatment is further included, and the method of the post-treatment is: acidification precipitation, filtration, washing, and drying to obtain the product. The reagent used in the washing is ice water or dilute hydrochloric acid. The drying temperature is 70-80℃.

[0029] In the present application, the purpose of the post-treatment is to convert the residual sulfonyl chloride group into a sulfonic acid group through hydrolysis.

[0030] The present application provides a preparation method of the phthalocyanine sulfonamide derivative dye, which comprises mixing a benzene derivative containing a sulfonamide group, urea, a metal salt, and a catalyst, and then performing a ring closure reaction to obtain the phthalocyanine sulfonamide derivative dye.

[0031] In the present application, the benzene derivative containing a sulfonamide group includes phthalic acid-4-sulfonamide and / or 1,2-dibromobenzene-4-sulfobenzamide, and is preferably phthalic acid-4-sulfonamide.

[0032] In the present application, the metal salt is preferably zinc chloride.

[0033] In the present application, the catalyst includes boric acid and / or ammonium molybdate, and is preferably boric acid.

[0034] In the present application, the mass ratio of the benzene derivative containing a sulfonamide group, urea, a metal salt, and a catalyst is 80-120:250-350:20-30:2-6, preferably 90-110:280-320:23-27:3-5, and further preferably 100:300:25:4.

[0035] In the present application, the temperature of the ring closure reaction is 150-210℃, preferably 170-200℃, and further preferably 180-190℃; and the time of the ring closure reaction is 8-10h, preferably 8.5-9.5h, and further preferably 9h.

[0036] The present application further provides an application of the phthalocyanine sulfonamide derivative dye in a photoresist or a display panel pigment.

[0037] In the present application, the phthalocyanine sulfonamide derivative dye and the dispersion are mixed.

[0038] In the present application, the addition amount of the phthalocyanine sulfonamide derivative dye is 0.5-1% of the mass of the dispersion.

[0039] In the present application, the dispersion is a photoresist.

[0040] The technical solutions provided by the present application will be described in detail below in conjunction with the embodiments, but they should not be understood as limiting the scope of protection of the present application.

[0041] Example 1

[0042] Mix 57.5 parts of zinc phthalocyanine and 205 parts of chlorosulfonic acid, and heat to 130°C. Add 98 parts of thionyl chloride and react at 137°C. After 3 hours, the reaction is complete. Cool and pour into ice water. Filter to obtain phthalocyanine sulfonamide chloride. Dissolve 49 parts of 3-(2'-ethylhexyloxy)-propyl-1-amine in 1000 parts of water, adjust the pH to 7.5 with acetic acid, and add 10 parts of phthalocyanine sulfonamide chloride to carry out the amination reaction. The amination reaction temperature is 55°C, and the amination reaction time is 2 hours. After the reaction is complete, filter, then wash with 1500 parts of water. After washing is complete, dry at 75°C to obtain zinc phthalocyanine-3-(2'-ethylhexyloxy) propyl sulfonamide disulfonic acid.

[0043] Mix zinc phthalocyanine-3-(2'-ethylhexyloxy) propyl sulfonamide disulfonic acid prepared in Example 1 and photoresist dispersion with an additive amount of 0.5% of the mass of the dispersion to obtain a photoresist pigment.

[0044] The particle size of the photoresist pigment prepared in Example 1 is reduced from 120 nm to 50 nm compared with the pigment without adding the phthalocyanine sulfonamide derivative dye.

[0045] Example 2

[0046] Mix 100 parts of phthalic acid-4-sulfonamide, 300 parts of urea, 25 parts of zinc chloride, 2 parts of boric acid, and 2 parts of ammonium molybdate, and carry out a ring closure reaction at 185°C. After 9 hours, the reaction is complete. Dissolve the reaction product in a hot dilute caustic soda solution, filter to remove zinc, and perform sodium salt precipitation with sodium chloride to obtain a sodium salt. Dry to obtain zinc phthalocyanine dodecyl sulfonamide.

[0047] Mix zinc phthalocyanine dodecyl sulfonamide prepared in Example 2 and photoresist dispersion with an additive amount of 1% of the mass of the dispersion to obtain a photoresist pigment.

[0048] The brightness of the photoresist pigment prepared in Example 2 is improved by 2 levels compared with the pigment without adding the phthalocyanine sulfonamide derivative dye.

[0049] Example 3

[0050] Compared with Example 1, the difference is that in Example 3, 40 parts of dodecyl amine is dissolved in 100 parts of water, the pH is adjusted to 7.5 with acetic acid, and 10 parts of phthalocyanine sulfonamide chloride is added to carry out the amination reaction.

[0051] Mix zinc phthalocyanine dodecyl sulfonamide prepared in Example 3 and photoresist dispersion with an additive amount of 1% of the mass of the dispersion to obtain a photoresist pigment.

[0052] The photoresist pigment prepared in Example 3 has a regular porous structure compared with the pigment without adding the phthalocyanine sulfonamide derivative dye.

[0053] Example 4

[0054] After mixing 46 parts of zinc phthalocyanine and 164 parts of chlorosulfonic acid, the mixture was heated to 110°C, 78.4 parts of thionyl chloride was added, and the reaction was carried out at 123°C. After 5 hours, the reaction was completed, and after cooling, the product was poured into an ice water mixture, and the phthalocyanine sulfuryl chloride was obtained by filtration. After dissolving 20 parts of 2-hydroxyethylamine in 800 parts of ethanol, the pH was adjusted to 8.2 with acetic acid, and 10 parts of phthalocyanine sulfuryl chloride was added for amination reaction. The amination reaction was carried out at a temperature of 35°C for 6 hours. After the reaction was completed, the pH was adjusted to 3, and the precipitate was separated by filtration. After washing with dilute hydrochloric acid for 3 times, the product was dried at 75°C under vacuum to obtain zinc phthalocyanine-2-hydroxyethyl sulfonamide monosulfonic acid.

[0055] The product prepared in Example 4 has both water solubility and organic solvent solubility.

[0056] The zinc phthalocyanine-2-hydroxyethyl sulfonamide monosulfonic acid prepared in Example 4 was added to the photoresist dispersion at a dosage of 0.5% of the mass of the dispersion, and a photoresist pigment was obtained.

[0057] The photoresist pigment prepared in Example 4 has a green 2 level compared with the pigment without adding the phthalocyanine sulfonamide derivative dye.

[0058] Comparative Example 1

[0059] After mixing 57.5 parts of zinc phthalocyanine and 205 parts of chlorosulfonic acid, the mixture was reacted at 130°C for 3 hours. After cooling, it was poured into ice water, neutralized to pH=7 with sodium hydroxide solution, washed and dried after filtration to obtain zinc phthalocyanine disulfonic acid.

[0060] The zinc phthalocyanine disulfonic acid prepared in Comparative Example 1 does not have a sulfonamide group, and can only be dissolved in water and dilute alkali solution, and is almost insoluble in organic solvents such as ethanol and chloroform. When used for photoresist preparation, the dispersion particle size is too large, the stability is poor, and it cannot meet the application requirements of organic systems.

[0061] Comparative Example 2

[0062] Under stirring, 140g of 20% mass fraction oleum was slowly added to 20g of zinc phthalocyanine. After stirring uniformly in a closed environment, the temperature was raised to 65°C, and the reaction was carried out for 6 hours. After natural cooling to room temperature, the sulfonated crude product was precipitated in a mixture of 500g of ice water. After filtration, the product was dissolved in sodium hydroxide solution, the pH was adjusted to >12, and then filtered. After adjusting the pH to <1.5 with hydrochloric acid, the product was washed with water and 80% ethanol to obtain a fine product with a yield of 18.64 and a recovery rate of 82%. The sulfonated zinc phthalocyanine was determined by solid state mass spectrometry to have an average sulfonation rate of about 1.0.

[0063] The product of Comparative Example 2, although soluble in organic solvents, lacks developing performance and cannot achieve precise pattern formation when used in the preparation of a display panel photoresist.

[0064] Comparative Example 3

[0065] After mixing 10 parts of zinc phthalocyanine with 65 parts of 25% mass fraction oleum, a sulfonation reaction was carried out at 150°C, and the reaction was completed after 6 hours. After neutralization and salting-out purification, a zinc phthalocyanine tetrasulfonic acid product was obtained.

[0066] The product prepared in Comparative Example 3, although having excellent water solubility, has extremely poor dispersibility in organic media, is prone to agglomeration, and the prepared photoresist dispersion has poor uniformity and insufficient color stability, with a light fastness reduced by more than 30% compared to Example 1 of the present application.

[0067] As can be seen from the above examples, the present application provides a phthalocyanine sulfonamide derivative dye, a preparation method and application thereof. The structure general formula of the phthalocyanine sulfonamide derivative dye is: (PC)-(SO2-N-X) z -(SO3R) y wherein PC is a phthalocyanine or metal phthalocyanine group, X is hydrogen, C1-C14 alkyl, hydroxyalkyl, aralkyl or an aromatic group, R is hydrogen, C1-C4 alkyl or an amine salt cation, z has a value in the range of 1-4, y has a value in the range of 1-3, and z+y≤4. By simultaneously introducing a sulfonamide group and a sulfonic acid group, the prepared derivative dye has excellent organic solvent solubility and water solubility, effectively solving the problem of single solubility of traditional zinc phthalocyanine dyes.

[0068] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered within the scope of protection of the present application.

Claims

1. A phthalocyanine sulfonamide derivative dye, characterized in that, The general structural formula of the phthalocyanine sulfonamide derivative dye is: (PC)-(SO2-NX). z -(SO3R) y , Wherein, PC is a phthalocyanine or metal phthalocyanine group, X is hydrogen, C1-C14 alkyl, hydroxyalkyl, aralkyl or aromatic group, R is hydrogen, C1-C4 alkyl or amine salt cation, z ranges from 1 to 4, y ranges from 1 to 3, and z+y≤4.

2. The phthalocyanine sulfonamide derivative dye according to claim 1, characterized in that, When the PC is a metal phthalocyanine group, the metal includes copper, zinc, nickel, or cobalt.

3. A method for preparing a phthalocyanine sulfonamide derivative dye according to claim 1 or 2, characterized in that, Includes the following steps: 1) Phthalocyanine compounds, chlorosulfonic acid, and thionyl chloride are reacted to obtain phthalocyanine sulfonyl chloride; 2) Amination reaction of phthalocyanine sulfonyl chloride and amine compounds in a solvent to obtain phthalocyanine sulfonamide derivative dyes.

4. The method for preparing phthalocyanine sulfonamide derivative dyes according to claim 3, characterized in that, The mass ratio of the phthalocyanine compound, chlorosulfonic acid and thionyl chloride is 40~65:160~220:75~105; The mass ratio of phthalocyanine sulfonyl chloride, amine compound and solvent is 5~15:35~55:100~1200.

5. The method for preparing phthalocyanine sulfonamide derivative dyes according to claim 4, characterized in that, In step 1), the phthalocyanine substance is phthalocyanine or metallic phthalocyanine; The reaction temperature is 90~138℃, and the reaction time is 3~8h.

6. The method for preparing phthalocyanine sulfonamide derivative dyes according to claim 4 or 5, characterized in that, In step 2), the amine compound includes one or more of propanol-1,3-diamine, 3-(2'-ethylhexyloxy)-propyl-1-amine, dodecylamine, and aniline; The solvent includes one or more of water, ethanol, pyridine, and nitrobenzene; The amination reaction is carried out at a temperature of 20-60°C, for a time of 1-12 hours, and at a pH of 5.6-9.

6.

7. A method for preparing a phthalocyanine sulfonamide derivative dye according to claim 1 or 2, characterized in that, A sulfonamide derivative dye is obtained by mixing a benzene derivative containing a sulfonamide group, urea, a metal salt, and a catalyst and then carrying out a ring-closure reaction.

8. The method for preparing phthalocyanine sulfonamide derivative dyes according to claim 7, characterized in that, The benzene derivatives containing sulfonamide groups include phthalic acid-4-sulfonamide and / or 1,2-dibromobenzene-4-sulfonamide; The metal salt includes zinc chloride; The catalyst includes boric acid and / or ammonium molybdate; The mass ratio of the benzene derivative containing sulfonamide groups, urea, metal salt and catalyst is 80~120:250~350:20~30:2~6.

9. The method for preparing phthalocyanine sulfonamide derivative dye according to claim 8, characterized in that, The closed-loop reaction is carried out at a temperature of 150~210℃ for 8~10h.

10. The use of a phthalocyanine sulfonamide derivative dye as described in claim 1 or 2 in photoresist or display panel pigments.