WO2010075780A1

WO2010075780A1 - A weather resistance black dye and its preparation and use

Info

Publication number: WO2010075780A1
Application number: PCT/CN2009/076222
Authority: WO
Inventors: 彭孝军; 李少磊; 张剑洲; 樊江莉; 孙世国; 张蓉
Original assignee: 大连理工大学; 珠海纳思达企业管理有限公司
Priority date: 2008-12-31
Filing date: 2009-12-30
Publication date: 2010-07-08

Abstract

A black dye, its preparation and use are provided. It comprises formula (I) or its mixture, where in a=0-4, b=0-4, a+b=1-4; R₁, R₂ = H, C_1-18 alkyl, C_6-12 aryl, phenyl and naphthyl substituted by A, (CR₃R₄)nA or B. The dye has excellent weather resistance, light resistance, ozone resistance, and is used as colorant in printing ink, dope, lacquer, inkjet, marker, paper, textile, glass, chinaware or polymer.

Description

Weather resistant black dye and preparation method and use thereof

This invention relates to weatherable black dyes, and more particularly to a novel weatherable black dye and its preparation and use. Background technique

Digital inkjet inks are classified into pigment inkjet inks and dye-based inkjet inks. Among them, pigment inkjet inks emit images with light, ozone and water fastness, but they are difficult to process and easy to block. The shortcomings of the ink head, the color is not bright enough and the cost is high, which limits its application. Compared with pigment inkjet inks, dye inkjet inks have the following advantages.

(1) It has good permeability, wear resistance and stability, and it is not easy to block the print head.

(2) The color is bright, the dye used is complete, and the range is wide.

(3) Since more than 60% of the components are water, the cost is relatively low and meets environmental protection requirements.

For the above reasons, dye-based inkjet inks have been the mainstream products in the market. However, dye-type ink-jet inks have defects in weather resistance due to the problem of the structure of the dye itself, such as poor light resistance and oxidation resistance, and its water fastness is not as good as that of pigment-based inks, and improvement is required.

At present, the most popular black inkjet dyes for inkjet printing on the market are C.I. Direct Black 154, C.I. Direct Black 171, C.I. Direct Black 168, C.I. Direct Black 19, C.I. Food Black 2, C.I. Acid Black 1, and its structure is as follows. 4

CI Direct Black 171

CI Acid Black 1 Black inkjet inks formulated from one or more of the above black dyes have poor light resistance and ozone resistance, and the printed images and characters are poor in durability, which cannot satisfy the market for high quality images and text. demand.

The Swiss company Clariant (US 6464768) has introduced the following structural dyes. Although it has high light fastness and excellent neutral black tone, the dye is easy to aggregate due to its high molecular weight and the conjugate chain is too long. Not good, and it contains heavy metal copper ions that are toxic.

US20070240608A1 describes adding a certain amount of terpenoids to the ink, which is effective The ink is improved in ozone resistance, but the quinone compound has a great influence on the pH of the ink, and the quinone compound acts on the water-soluble sulfonic acid group to deteriorate the stability of the ink.

In addition, US6423375 teaches that the light fastness of the ink can be effectively improved by adding an inorganic salt (such as KI, Nal, Na ₂ S ₂ O ₃ ) to the coated paper.

However, none of the above patents solves the problem of poor weather resistance (including light resistance and ozone resistance) of dyes and their inks. Summary of the invention

The object of the present invention is to develop a series of black dyes having excellent weather resistance (including light resistance and ozone resistance) and water resistance.

In a first aspect of the invention, there is provided a series of dyes having a novel structure comprising a compound of formula (I) or a mixture thereof, which has excellent weatherability, including light fastness and ozone fastness, and excellent Water fastness:

(I) where: a=0 - 4, b = 0 -4, a+b is l-4; a and b cannot be zero at the same time;

1 and R ₂ are the same or different H, (^ _-18 alkyl, C ₆ _-12 aryl, substituted A phenyl or naphthyl, (CR ₃ R4) „A, or B ; A is H, OH, NH ₂ , CO ₂ M", SO ₃ M" or OSO ₃ M", n is 0-18; R ₃ and each are the same or different H or d ₄ alkyl;

R ₅ and R _{6 in} B may be the same or different and are selected from the group consisting of: F, Cl, Br, OH, NH ₂ , NHCN, N(CH ₃ ) ₂ , NHCONH ₂ , NH(CR ₃ R4) „A, N(( CR ₃ R4) „A) ₂ , NR ₃ A ₂ , SH, or S(CR ₃ R4) „A; A ₂ is a phenyl or naphthyl group having 1-5 substituents A ₃ ; A _{3 is} selected from the group consisting of H, Cl, Br, CN, CF ₃ , CH ₃ , NO ₂ , NH ₂ , SO ₃ M, CO ₂ M,,, PO ₃ M,, ₂ , or PO ₃ HM,,;

M, M" are each independently H, a metal ion, an ammonium salt, or an organic ammonium salt, and M, and M" may be the same or different.

In a preferred embodiment of the dye of the present invention, the M, and M" are each independently H,

Na, K, Li, NH ₄ , N(CH ₃ ) ₄ , NH(CH ₃ ) ₃ , NH ₂ (CH ₃ ) ₂ , NH ₃ (CH ₃ ) ₄ , NH(CH ₂ CH ₂ OH) ₃ , NH ₂ (CH ₂ CH ₂ OH) ₂ or NH ₃ CH ₂ CH ₂ OH.

In another preferred embodiment, wherein b is 0 and a is 1-4.

In another preferred embodiment, wherein a+b is 2-4.

In another preferred embodiment, wherein said R and R ₂ are the same or different H or

Ci_4 焼 base.

A second aspect of the invention relates to a process for the preparation of a black dye compound of the formula (I) which comprises:

First, the compound is synthesized by the following polyhydrazine reaction process.

Compound ( 1 ₀ )

Then, the compound (i _Q ) is further reacted with chlorosulfonic acid and a chlorinating reagent to obtain a structural formula (II); and then, the active acyl chloride group in the formed compound of the formula (Π) is subjected to basic hydrolysis to obtain a structural formula (i). a dye compound of I), or reacted with ammonia or an amine compound, and then neutralized with a base to obtain a dye compound of the formula (I); X in the formula (II) is not less than 2;

(ID) In a preferred embodiment of the method, wherein the molar ratio of the chlorosulfonic acid to the compound (I _Q ) is from 20 to 2000:1; the chlorinating reagent is preferably POCl ₅ , PC1 ₅ , PC1 _{3 and} SOCl ₂ , more preferably SOCl ₂ ; the molar ratio of the chlorinating reagent to the compound (I _Q ) is 2-500:1, and the reaction temperature is between 50 and 250 °C.

In a third aspect of the invention, there is provided a process for the preparation of a black dye compound of the formula (I) wherein b is 0, which comprises:

Compound (I ₀ ) Then, the compound (I _Q ) is reacted with sulfuric acid to obtain a structural formula (πι), which is then neutralized with a base to obtain a dye compound of the formula (I) wherein b is 0; y is not less than 2;

(III) In a preferred embodiment of the method, the molar ratio of the sulfuric acid to the compound (I _Q ) is 5 to 6000: 1, and the reaction temperature is 20 to 250 ° C.

In a fourth aspect of the invention, the invention relates to an ink comprising: the above dye of the invention.

In a preferred embodiment of the ink, the ink is a printing ink, a coating ink, or an inkjet ink. The inkjet ink is preferably a water-based inkjet ink, and may also preferably be a solvent-based inkjet ink.

In a fifth aspect of the invention, the invention relates to an inkjet aqueous ink composition comprising: 1-20% by weight of the above dye, 5-50% by weight of a water-miscible organic solvent, and 30-94% by weight of water, Based on the total weight of the composition.

In a preferred embodiment of the ink composition, the water-miscible organic solvent is selected from one or more of the following: ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol , triethylene glycol, glycerin, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol, butanediol, pentanediol, hexanediol, diglycerin, 2- Pyrrolidone and N-methyl-2-pyrrolidone.

In a sixth aspect of the invention, there is provided a coating comprising the above dye of the invention. The coating is preferably an outdoor coating.

In a seventh aspect of the invention, there is provided a lacquer comprising the above dye of the invention. The lacquer is preferably an exterior paint.

In an eighth aspect of the invention, the invention relates to a toner for laser printing comprising the above-mentioned dye of the invention α

In a ninth aspect of the invention, the invention relates to a marker comprising: the above dye of the invention.

In a tenth aspect of the invention, the use of the dye of the invention is used as a colorant in the following materials: inks, paints, lacquers, laser-printed toners, or markers.

In an eleventh aspect of the invention, the use of the dye of the invention is used as a colorant in the following materials: paper, fabric, glass, ceramic, or polymer. The fabric described therein is preferably selected from the group consisting of: woven fabrics, knitted fabrics or nonwoven fabrics. The polymeric material is preferably selected from the group consisting of rubber, plastic or fiber. detailed description

The weatherable black dye of the present invention comprises a compound of formula (I) or a mixture thereof. It preferably consists of a compound of formula (I) or a mixture thereof.

(I)

In the dye compound of the formula (I) of the present invention: a = 0 - 4, b = 0 - 4, a + b is 1-4; a and b cannot be simultaneously zero.

! And R ₂ are the same or different H, (^ _-18 alkyl, C ₆ _-12 aryl, substituted A phenyl or naphthyl, (CR ₃ R4) „A, or ^

Eight of them are 11, OH, NH ₂ , CO ₂ M" or SO ₃ M" or OSO ₃ M".

n is 0-18. n is preferably 0-10, more preferably 0-6, still more preferably 1-4. The smaller the value of n, the better the water solubility of the dye.

The alkyl group is preferably a d- ₁₆ alkyl group, more preferably a Cwo alkyl group, more preferably a d- ₆ alkyl group, still more preferably a d- ₄ alkyl group. The lower the number of C atoms of the alkyl group, the better the water solubility of the dye. When the sum is an aryl group of C ₆ _-12 , a phenyl group or a naphthyl group having a substituent A, the water solubility of the dye is deteriorated, and the solvent solubility is improved.

R ₃ and each are the same or different H or C _w alkyl groups.

R ₅ and R _{6 in} B may be the same or different and are selected from the group consisting of: F, Cl, Br, OH, NH ₂ , NHCN, N(CH ₃ ) ₂ , NHCONH ₂ , NH(CR ₃ R4) „A, N(( CR ₃ R4) „A) ₂ , NR ₃ A ₂ , SH, or S(CR ₃ R4) „A. A is as defined above.

A ₂ is 1-5 substituents having a phenyl or naphthyl group A _3, preferably with 1-3 substituents A _3, still more preferably with 1-2 substituents A _3; A ₃ is selected from H , Cl, Br, CN, CF ₃ , CH ₃ , NO ₂ , NH ₂ , SO ₃ M", CO ₂ M", PO ₃ M" ₂ , or PO ₃ HM"; preferably selected from H, Cl, Br, CN, CF ₃ , CH ₃ , NH ₂ , SO ₃ M", or PO ₃ M".

M', M"3⁄4 H, metal ion, ammonium salt, or organic ammonium salt. M' and M" may or may not be Same.

Preferably, M, M "is H, Na, K, Li, NH ₄ , N(CH ₃ ) ₄ , NH(CH ₃ ) ₃ , NH ₂ (CH ₃ ) ₂ , NH ₃ (CH ₃ ) ₄ , NH ( CH ₂ CH ₂ OH) ₃ , NH ₂ (C 3⁄4CH ₂ OH) ₂ or NH ₃ CH ₂ C 3⁄4 OH. More preferably, H, Na, Li, N(CH ₃ ) ₄ , NH(CH ₂ CH ₂ OH) ₃ is more preferred. NH ₂ (CH ₂ CH ₂ OH) ₂ or NH ₃ CH ₂ CH ₂ OH.

The present invention provides two processes for preparing a black dye compound of the formula (I), which are first synthesized by the following multiple reaction.

Compound (I ₀ ) Method (1): Compound (1) is further reacted with chlorosulfonic acid and a chlorinating reagent to obtain a structural formula (π), and then the resulting active acid chloride is hydrolyzed with a base to give a structural formula (I). a dye compound, or reacted with ammonia or an amine compound, and finally neutralized with a base to obtain a dye compound having the structural formula (I);

(II) where X is 1-4.

(II)

Wherein, the molar ratio of chlorosulfonic acid to the compound (1.) is 20-2000: 1, preferably 25-50: 1, more preferably 25- 45:1; The reaction temperature is between 50 and 250 ° C, preferably 80 to 230 ° C, more preferably 100 to 200 ° C, still more preferably 120 to 180. C, further preferably between 140-160 °C.

The chlorinating agent is preferably POCl ₅ , PC1 ₅ , PC1 ₃ and SOCl ₂ , more preferably SOCl ₂ ; the molar ratio of the chlorinating reagent to the compound (I _Q ) is 2 to 500: 1, more preferably 2 to 400:1. Further preferably, it is 2-300:1, more preferably 2-100:1, still more preferably 3-50:1, still more preferably 3-10:1, still more preferably 3-6:1.

The amine compound preferably has a water-soluble group, including but not limited to: a sulfonic acid group, a phosphoric acid group, a hydroxyl group or the like. These water soluble groups help to impart water solubility to the product.

The amine compound is preferably a primary amine, a secondary amine or a tertiary amine compound, and more preferably a primary amine compound. Specific examples of the amine compound include, but are not limited to, sulfuric acid, glycine, p-aminobenzenesulfonic acid and the like. Method (2): The compound (I _Q ) is reacted with sulfuric acid to obtain a structural formula (111), which is then neutralized with a base to obtain a dye compound of the structural formula (I) wherein b is 0; wherein y is 1 in the formula (III) -4.

(III) wherein the molar ratio of sulfuric acid to compound (1) is from 5 to 6000: 1, preferably from 5 to 3,000: 1, more preferably from 5 to 1000: 1, still more preferably from 6 to 500: 1, still more preferably from 7 to 300: Further preferably, it is 8-200:1, further preferably 10-100:1, further preferably 15-90:1, still more preferably 20-80:1, still more preferably 20-60:1, still more preferably 30-50:1 Preferably, the reaction temperature is 20 to 250 ° C, more preferably 50 to 230 ° C, still more preferably 80 to 200 ° C, still more preferably 100 to 180 ° C, still more preferably 100 to 150 ° C _; Use concentrated sulfuric acid or fuming sulfuric acid.

The resulting dye product is further purified prior to use to remove impurities such as inorganic salts such as NaCl, Na ₂ SO ₄ and the like. When the dye is used for a colorant in an inkjet ink, too many impurities such as an inorganic salt such as NaCl or Na ₂ SO _{4 may} greatly affect the storage stability of the ink, and the high-conductivity ink may burn off the nozzle. Therefore, before use, it is necessary to remove impurities such as inorganic salts such as NaCl and Na ₂ SO ₄ by ion exchange or reverse osmosis.

The dyes of the present invention have excellent UV and O ₃ resistance.

The dye of the present invention can be used in a wide variety of applications where weather resistance is required. For example, weather-resistant inks, paints, lacquers, markers, and laser-printed toners for outdoor use are used as colorants. The ink includes Printing inks, coating inks, inkjet inks, and the like. The inkjet ink can be a water based inkjet ink or a solvent based inkjet ink.

It can also be used in a variety of outdoor materials, as a coloring agent, to provide long-term color retention and fading. Such materials include, without limitation: paper, fabric, glass, ceramic, or polymer. The fabric comprises: a woven fabric, a knitted fabric or a nonwoven fabric, the polymer comprising plastic, rubber or fiber, and the like.

Further, the dye of the present invention has not only an unexpectedly good weather resistance for use outdoors, but also long-term stability and long-term storage property when it is used indoors. Whether the dye is exposed to air and light after application, or the dye is in storage prior to application, it has long-term color stability and is not susceptible to fading.

When used indoors, it can be used in the above inks, paints, lacquers, markers, laser printing toners, and various materials, used as colorants to make the inks, paints, paints, markers, laser prints Toners, and various materials have unexpectedly good color stability during long-term storage and are not easily faded. For example, when it is formulated into an inkjet ink together with other auxiliaries, the ink has long-term color stability even when it is in contact with air (such as oxygen and nitrogen) and light in the storage period before application. , not easy to fade. When the ink is used outdoors, it also has unexpectedly good weather resistance.

In a specific example, an aqueous inkjet ink composition is formulated with the dye of the present invention according to the following formulation: comprising: 1-20% by weight of the dye of the invention, 5-50% by weight of water-miscible organic the solvent and _30-94% by weight of water, based on the total weight of the composition as a reference. The water-miscible organic solvent described therein is preferably selected from one or more of the following: ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, ethylene Alcohol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol, butanediol, pentanediol, hexanediol, diglycerin, 2-pyrrolidone and N-methyl-2-pyrrolidone .

Various other conventional auxiliaries such as surfactant (0-3%), ultraviolet absorbing agent (0-3%), antioxidant (0-3%), and preservative (0) may optionally be added to the ink. -3%), bactericide (0-3%), pH adjuster (0-3%), metal ion complexing agent (0-2%), humectant (0-15%), driers (0 -5%), water repellent (0-5%), etc. Commonly used surfactants such as nonionic surfactants, anionic surfactants, polymeric surfactants, cationic surfactants, amphoteric surfactants, and the like.

The above-mentioned various types of auxiliaries are described in many existing monographs and patents, such as various surfactants, ultraviolet absorbers, such as those described in U.S. Patent No. 7,034,149, US Pat. No. 6,068,955, US Pat. No. 6,419,722, US Pat. No. 6,235,097, US Pat. No. 7,087,107, US Pat. No. 7,087,107, US Pat. Antioxidants, preservatives, fungicides, pH adjusters, metal ion complexing agents, humectants, driers, water repellents.

The ink is formulated using conventional methods in the inkjet ink industry. When the ink is prepared, it needs to be stirred and heated. It was then filtered through a microporous membrane (pore size 0.02-0.8 μηι) at 0-30 atmosphere.

The ink has a long-term storage even before contact with gas and light in the air during storage before use. The color stability is not easy to fade. After the ink is jet printed onto the medium, the resulting image also has long-term color stability.

The formulated inkjet ink composition is low in cost, excellent in weather resistance of printed images, and resistant to uv and anti-UV

0 ₃ performance is close to or exceeds the original original type of product ink. And has the following advantages:

- High ecological standards, free of heavy metals.

- Smooth printing, long standby time, no plugging.

- The ink has good permeability and the formed image has excellent wear resistance and water fastness.

-Good storage stability, excellent light and ozone resistance.

EXAMPLES Example 1 Synthesis of Compound (2)

Add 1000 parts of chlorosulfonic acid to a three-necked bottle of dry lOOmL, weigh 200 parts of compound (1 _Q ) and slowly add it to chlorosulfonic acid. The temperature is controlled at 50 ° C. After the addition, the temperature is raised to 70 _ 80. °C, stir for one hour, then slowly heat up to 140 - 150 ° C, keep warm for 10 hours, then cool to 70 ° C, add 112 parts of thionyl chloride, warm to 80-85 ° C, keep warm for two hours, After cooling to room temperature, the reaction was slowly injected into a 4 L ice-water mixture, the temperature was controlled at 0 - 5 ° C, filtered, and washed with ice water until the pH of the filtrate was greater than 4, and the obtained filter cake 400 was heated in water to 80 - The reaction was stirred at 90 ° C for two hours and then neutralized with sodium hydroxide to a pH of 10. The salt was added in an amount of 200 g of sodium chloride per liter of the reaction volume, and the solid was washed with a 20% sodium chloride solution, and then washed with a small amount of water to obtain 220 parts of a black compound (2).

The obtained dyes were separated by high performance liquid chromatography (HPLC) to reveal three main product peaks, which were separated by HPLC.

Compound 2-l: n=2;

Compound 2-2: n=3; Compound 2-3: n=4;

The molecular molar mass of compound 2-1 (n=2) should be 869.0 (Μ' in terms of Na), detected by electrospray ionization mass spectrometry (API-ES). In negative mode, electrospray mass spectrometry has a base peak with a mass-to-charge ratio of 411.5. , is the di-negative ion peak of the dye (molecular mass [M-2Na]/2), and has an anion peak of mass-charge ratio of 824.0 ([M+H-2Na]) and an anion peak of mass-to-charge ratio of 846 ([M -Na]), both prove that the molar mass M of the dye molecule is 869.0; the molar mass M of the compound 2-2 (n=3) should be 971.0 (Μ' in terms of Na), electrospray ionization mass spectrometry (API-ES) detection, In the negative mode, electrospray mass spectrometry has a mass-to-charge ratio of 300.7 (base peak, [M-3Na]/3), a mass-to-charge ratio of 451.5 ([M-3Na+H]/2), and a mass-to-charge ratio of 462.5 ([M- 2Na]/2) _; both prove that the molar mass M of the dye molecule is 971.0; the molecular molar mass M of compound 2-3 (n=4) should be 1073.0 (Μ' in terms of Na), electrospray ionization mass spectrometry (API-ES) detection In negative mode, electrospray mass spectrometry has a mass-to-charge ratio of 245.3 (base peak, [M-4Na]/4), 327.3 ([M+H-4Na]/3), 334.7 ([M-3Na]/3) 491.5 ([M+2H-4Na]/2) 502.5 ([M+H-3Na]/2), all proved that the molar mass M of the dye molecule was 1073.0.

X=

Compound

3 Li ⁺

Lithium hydroxide

4 K ⁺

Potassium hydroxide

5 ΝΗ ₄ ⁺

Ammonia

6

Triethanolamine ⁺ ΝΗ (CH ₂ CH ₂ OH) 3

7 ⁺ NMe ₄

Tetramethylammonium hydroxide

Example 3 Synthesis of Compound (8)

Add 1000 parts of chlorosulfonic acid to a three-necked bottle of 100 mL of dryness, and slowly add 200 parts of compound (1) to chlorosulfonic acid. The temperature is controlled at 50 ° C. After the addition, the temperature is raised to 70-80 ° C. , stirring for one hour, then slowly warming to 140 - 150 ° C, holding for 6 hours, then cooling to 70 ° C, adding 112 parts of dichloro Sulfoxide, warmed to 80-85 ° C, kept for two hours, cooled to room temperature, then slowly inject the reaction into 4L ice water mixture, control the temperature at 0_5 ° C, filter, ice water wash, until the filtrate pH is greater than 4 The obtained filter cake was suspended in 1000 mL of ice water, 28.7 parts of taurine was added, and the reaction was stirred at 0 - 5 ° C for two hours, and the aqueous solution of NaOH was added dropwise to maintain the pH at 8.0-8.5, and then the temperature was raised to 40 - 45 ° C. For two hours, the pH was controlled at 8.0-8.5, then neutralized with sodium hydroxide to pH 10, and the temperature was raised to 80-90 ° C for two hours. The salt was added in an amount of 200 g of sodium chloride per liter of the reaction volume, and the solid was washed with a 20% sodium chloride solution, and then washed with a small amount of water to obtain 180 parts of a black compound (8).

The obtained dye was separated by high performance liquid chromatography (HPLC) to reveal four main product peaks, which were separated by HPLC:

Compound 8-l: a = l, b = l;

Compound 8-2: a = l, b = 2 _;

Compound 8-3: a = 2, b = l;

Compound 8-4: a = 3, b = l;

Compound 8-1, a=l, b=l, molecular molar mass M should be 976.0, electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray mass spectrometry has a mass-to-charge ratio of 465.0 (base peak, [M -2Na]/2), 931.0( [M-2Na+H] ), both proved that the molar mass M of the dye molecule is 976.0, which is in agreement with the theoretical value; compound 8-2, a=l, b=2, molar mass of dye molecule It should be 1185.0, electrospray ionization mass spectrometry (API-ES). In negative mode, electrospray ionization mass spectrometry has a mass-to-charge ratio of 569.5 (base peak [M-2Na]/2), which is in agreement with the theoretical value; compound 8-3, a=2, b=l, molecular molar mass M should be 1078.0, electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray mass spectrometry has a mass-to-charge ratio of 336.3 (base peak, [M-3Na]/ 3), 505.0 ([M-3Na+H]/2), 516.0 ([M-2Na]/2), both proved that the molar mass M of the dye molecule is 1078.0, which is in agreement with the theoretical value; compound 8-4, a=3 , b=l, molecular molar mass M should be 1180.0, electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray mass spectrometry has a mass-to-charge ratio of 370.3 (base peak, [M-3Na]/3), 272.0 ( [M-4Na]/4), 556.0 ( [M-3Na+H]/2 ), all proved the molar mass of the dye molecule M It is 1180.0, which is in agreement with the theoretical value.

Example 4 Synthesis of Compound (9)

Where a+b = 2-4.

Compound I _Q (67 parts) was added portionwise to 340 parts of chlorosulfonic acid, stirred at 140-150 ° C for 4 hours, cooled to 50 ° C, and then added with 37 parts of thionyl chloride at 70-80 The reflux reaction was continued for 1 hour at °C. After cooling to room temperature, it was poured into 2000 parts of ice water, filtered, and the filter cake was washed three times with 500 parts of ice water to obtain 530 parts of a dye wet cake.

Cyanuric chloride (36 parts), aniline-2,5-disulfonic acid disodium salt (60 parts) was added to 800 parts of water, reacted under stirring at 0-5 ° C for 5 hours, and added with NaHCO ₃ aqueous solution. The pH of the reaction system is between 8 and 9. Then, it was further reacted at room temperature for 1 hour. Ethylenediamine (12 parts) was added, the temperature was raised to 40-45 ° C, and the aqueous solution of NaHCO _{3 was} added dropwise to control the pH of the reaction system at 8-9, and the reaction was stirred at this temperature for 5 hours. Then, the mixture was cooled to 30 ° C, the above chlorosulfonated filter cake was added, 1000 parts of ice water was added, and the reaction was stirred at 40-45 ° C, while 10% aqueous NaOH solution was added dropwise to control the pH of the reaction system at 8-9, and stirred for 3 hours. , gradually increase the temperature and react at 50-55 ° C for 1 hour. Finally, it was cooled to 40 ° C, and the pH was adjusted to 9-10 with a 10% aqueous NaOH solution, and filtered to remove possible insoluble impurities. The salt was added in an amount of 200 g of sodium chloride per liter of the reaction volume, and the solid was washed with a 20% sodium chloride solution, and then washed with a small amount of water to obtain 70 parts of a black compound (9).

The obtained compound (9) was separated into four main product peaks by high performance liquid chromatography and isolated by HPLC: compound 9-1: a=l, b=l;

Compound 9-2: a = 2, b = l;

Compound 9-3: a = l, b = 2 _;

Compound 9-4: a = 3, b = l;

Electrospray ionization mass spectrometry (API-ES) detection, in the negative mode, the compound molecular mass of the compound 9-1 is a=l, b=l, the theoretical molecular mass of the dye is 1297.0, and the electrospray ionization mass spectrometry has a mass-to-charge ratio of 409.3 (base peak, [ M-3Na]/3), 614.5 ([M+H-3Na]/2), both proved that the molar mass M of the dye molecule was 1297.0 in agreement with the theoretical value.

Compound 9-2, a=2, b=l, the theoretical molecular mass M of the dye is 1399.0, detected by electrospray ionization mass spectrometry (API-ES), and in the negative mode, the mass-to-charge ratio is 326.8 (base peak, [M-4Na] ]/4), 436.0 ([M+H-4Na]/3), 443.3 ([M-3Na]/3), 654.5 [M+2H-4Na]/2), all proved that the molar mass M of the dye molecule was 1399.0 , in line with the theoretical values.

Compound 9-3, a=l, b=2, the molar mass M of the dye molecule should be 1826.9, 1828.9 (isotopic peak), electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray mass spectrometry has mass charge Ratio 342.4, 342.8 (base peak, [M-5Na]/5), 428.2, 428.7 ([M+H-5Na]/4), 433.7, 434.2 ([M-4Na]/4), 571.3, 571.9 ([ M+2H-5Na]/3) 578.6, 579.3 ([M+H-4Na]/3), all proved that the molar mass M of the dye molecules was 1826.9, 1828.9 (isotope peak), which was in agreement with the theoretical value.

Compound 9-4, a=3, b=l, molecular molar mass M should be 1500.9, electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray mass spectrometry has a mass-to-charge ratio of 477.3 (base peak, [M -3Na]/3), 352.2 C [M-4Na]/4), 716.5 C [M-3Na+H]/2), both proved that the molar mass M of the dye molecule was 1501.0, which was in agreement with the theoretical value.

Compound Io (67 parts) was added portionwise to 340 parts of chlorosulfonic acid, stirred at 140-150 ° C for 4 hours, cooled to 50 ° C, and then added with 37 parts of thionyl chloride at 70-80 ° C was refluxed for 1 hour. After cooling to room temperature, it was poured into 2000 parts of ice water, filtered, and the filter cake was washed three times with 500 parts of ice water to obtain 530 parts of a dye wet cake.

Cyanuric chloride (36 parts), aniline-2,5-disulfonic acid disodium salt (60 parts) was added to 800 parts of water, reacted under stirring at 0-5 ° C for 5 hours, and added with NaHCO ₃ aqueous solution. The pH of the reaction system is between 8 and 9. Then, it was further reacted at room temperature for 1 hour. Ethylenediamine (12 parts) was added, the temperature was raised to 40-45 ° C, and the aqueous solution of NaHCO _{3 was} added dropwise to control the pH of the reaction system at 8-9, and the reaction was stirred at this temperature for 5 hours. Then, the mixture was cooled to 30 ° C, the above chlorosulfonated filter cake was added, 1000 parts of ice water was added, and the reaction was stirred at 40-45 ° C, while 10% NaOH aqueous solution was added dropwise to control the pH of the reaction system at 8-9, and stirred for 3 hours. , gradually increase the temperature and react at 50-55 ° C for 1 hour. Then, a 50% aqueous solution of monocyanamide (19 parts) was added, and the pH of the reaction system was controlled to be 8-9 by dropwise addition of 10% aqueous NaOH solution, and the temperature was gradually raised to 80-90 ° C, and the reaction was stirred at this temperature for 3 hours. Finally, it was cooled to 40 ° C, and the pH was adjusted to 9-10 with a 10% aqueous NaOH solution, and filtered to remove possible insoluble impurities. The salt was added in an amount of 200 g of sodium chloride per liter of the reaction volume, and the solid was washed with a 20% sodium chloride solution, and then washed with a small amount of water to obtain 68 parts of a black compound (10).

The obtained compound (10) was separated into three main product peaks by high performance liquid chromatography, and separated by HPLC:

Compound 10-1: a = l, b = l;

Compound 10-2: a = 2, b = l;

Compound 10-3: a = l, b = 2 _;

Compound 10-4: a = 3, b = l;

Electrospray ionization mass spectrometry (API-ES) detection, in the negative mode, in the structure of compound 10-1, a = l, b = l, the theoretical molecular mass of the dye is 1303.0, with a mass-to-charge ratio of 411.3 (base peak, [M-3Na] ]/3), 617.5 ([M+H-3Na]/2) all proved that the molar mass M of the dye molecule was 1303.0 in agreement with the theoretical value.

Compound 10-2, a=2, b=l, the theoretical molecular mass M of the dye is 1405.0, detected by electrospray ionization mass spectrometry (API-ES), and in the negative mode, the mass-to-charge ratio is 328.3 (base peak, [M-4Na ]/4), 438.0 ( [M+H-4Na]/3 ), 445.3 ([M-3Na]/3), 657.5 [M+2H-4Na]/2), all proved that the molar mass M of the dye molecule was 1405.0, which was in agreement with the theoretical value of 1405.0.

Compound 10-3, a=l, b=2, dye molecule molar mass M should be 1839.0, electrospray ionization mass spectrometry (API-ES) detection, in negative mode, mass-to-charge ratio 344.8 (base peak, [M-5Na ]/5), 431.2 ([M+H-5Na]/4), 436.7 ([M-4Na]/4), 575.3 ([M+2H-5Na]/3), 582.7 ([M+H-4Na ]/3), both proved that the molar mass M of the dye molecule was 1839.0, which was in agreement with the theoretical value of 1839.0.

Compound 10-4, a=3, b=l, molecular molar mass M should be 1507.0, electrospray ionization mass spectrometry (API-ES) detection, in negative mode, mass-to-charge ratio 479.3 (base peak, [M-3Na] /3) , 353.7 ([M-4Na]/4), 719.5 ([M-3Na+H]/2), all proved that the molar mass M of the dye molecule was 1507.0, which was in agreement with the theoretical value of 1507.0. Example 6

Synthesis of compound (11)

The aqueous solution of monocyanamide was changed to dimethylamine, and the other steps were the same as in Example 5 to give 50 parts of the compound (11). The obtained compound (11) was separated into three main product peaks by high performance liquid chromatography, and separated by HPLC:

Compound 11-1: a = l, b = l;

Compound 11-2: a=2, b=l;

Compound 11-3: a = l, b = 2 _; Compound 11-4: a = 3, b = l;

Electrospray ionization mass spectrometry (API-ES) detection, in the negative mode, the compound molecular weight of the compound 11-1 was a=l, b=l, the theoretical molecular mass of the dye was 1306.0, and the electrospray ionization mass spectrometry had a mass-to-charge ratio of 412.3 (base peak, [ M-3Na]/3), 619.0 ([M+H-3Na]/2) all proved that the molar mass M of the dye molecule was 1306.0 in agreement with the theoretical value.

Compound 11-2, a=2, b=l, the theoretical molecular mass M of the dye is 1408.0, detected by electrospray ionization mass spectrometry (API-ES), and in the negative mode, the mass-to-charge ratio is 329.0 (base peak, [M-4Na ]/4), 439.0 ([M+H-4Na]/3), 446.3 ([M-3Na]/3), 659.0 [M+2H-4Na]/2), all proved that the molar mass M of the dye molecule was 1408.0 , in accordance with the theoretical value of 1408.0. Compound 11-3, a=l, b=2, the molar mass M of the dye molecule should be 1845.1, detected by electrospray ionization mass spectrometry (API-ES). In the negative mode, electrospray mass spectrometry has a mass-to-charge ratio of 346.0 (base peak, [ M-5Na]/5), 431.25 ([M+H-5Na]/4), 432.8 ([M-4Na]/4), 577.4 ([M+2H-5Na]/3), 584.7 ([M+ H-4Na]/3), both proved that the molar mass M of the dye molecule was 1845.1, which was in agreement with the theoretical value.

Compound 11-4, a=3, b=l, molecular molar mass M should be 1510.0, electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray mass spectrometry has a mass-to-charge ratio of 480.3 (base peak, [M -3Na]/3), 354.5 ([M-4Na]/4), 721.0 C [M-3Na+H]/2), both proved that the molar mass M of the dye molecule was 1510.0, which was in agreement with the theoretical value. Example 7

Synthesis of compound (12)

Compound I _Q (67 parts) was added portionwise to 340 parts of chlorosulfonic acid, stirred at 140-150 ° C for 4 hours, cooled to 50 ° C, and then added with 37 parts of thionyl chloride at 70-80 The reaction was refluxed for 1 hour at ° C. After cooling to room temperature, it was poured into 2000 parts of ice water, filtered, and the filter cake was washed three times with 500 parts of ice water to obtain 530 parts of a dye wet cake.

Cyanuric chloride (36 parts), aniline-2,5-disulfonic acid disodium salt (60 parts) was added to 800 parts of water, reacted under stirring at 0-5 ° C for 5 hours, and added with NaHCO ₃ aqueous solution. The pH of the reaction system is between 8 and 9. Then, it was further reacted at room temperature for 1 hour. Ethylenediamine (12 parts) was added, the temperature was raised to 40-45 ° C, and the aqueous solution of NaHCO _{3 was} added dropwise to control the pH of the reaction system at 8-9, and the reaction was stirred at this temperature for 5 hours. Then cooled to 30 ° C, add the above chlorosulfonated filter cake, add 1000 parts of ice water, stir the reaction at 40-45 ° C, while adding 10% NaOH and 20% NH ₂ CH ₂ CH ₂ SO ₃ Na The aqueous solution of sodium taurate was used to control the pH of the reaction system at 8-9, stirred for 3 hours, and gradually heated at 50-55 ° C for 1 hour. Finally, it was cooled to 40 ° C, and the pH was adjusted to 9-10 with a 10% aqueous NaOH solution, and filtered to remove possible insoluble impurities. The salt was added in an amount of 200 g of sodium chloride per liter of the reaction volume, and the solid was washed with a 20% sodium chloride solution, and then washed with a small amount of water to obtain 48 parts of a black compound (12).

The obtained compound (12) was separated into three main product peaks by high performance liquid chromatography, and fractions were prepared by HPLC. Get:

Compound 12-1: a = l, b = l, c = 0;

Compound 12-2: a = l, b = l, c = l;

Compound 12-3: a = 2, b = l, c = l;

Electrospray ionization mass spectrometry (API-ES) showed that in the negative mode, the m/z peak of compound 12-1 had 409.3 (base peak, [M-3Na]/3), 614.5 ([M+H-3Na]/2 ), it is proved that the molar mass M of the dye molecule is 1297.0, which is in agreement with the theoretical value. The m/z peak of compound 12-2 is: 353.5 [(M-4Na)/4], 471.6 [(M-4Na+H)/3], 479.0 [(M-3Na)/3], 708.0 [(M -4Na+2H)/2], 719.0 [(M-3Na+H)/2], 730.0 [(M-2Na)/2], all proved that the molar mass M of the dye molecule was 1506.0, which was in agreement with the theoretical value. The m/z peak of compound 12-3 is: 373.47 [(M-5Na+H)/4], 379.0 [(M-4Na)/4], 747.9 [(M-5Na+3H)/2], 498.3 [ (M-5Na+2H)/3], 505.6 [(M-4Na+H)/3], both proved that the molar mass M of the dye molecule was 1607.9, which was in agreement with the theoretical value.

Example 8

Synthesis of Compound (13)

Cyanuric chloride (36 parts), aniline-2,5-disulfonic acid disodium salt (60 parts) was added to 800 parts of water, reacted under stirring at 0-5 ° C for 5 hours, and added with NaHCO ₃ aqueous solution. The pH of the reaction system is between 8 and 9. Then, it was further reacted at room temperature for 1 hour. Ethylenediamine (12 parts) was added, the temperature was raised to 40-45 ° C, and the aqueous solution of NaHCO _{3 was} added dropwise to control the pH of the reaction system at 8-9, and the reaction was stirred at this temperature for 5 hours. Then cooled to 30 ° C, add the above chlorosulfonated filter cake, add 1000 parts of ice water, add 18 parts of sodium p-aminobenzenesulfonate, stir the reaction at 40-45 ° C, while adding 10% NaOH aqueous solution to control The pH of the reaction system was 8-9, stirred for 3 hours, and gradually heated at 50-55 ° C for 4 hours. Finally, it was cooled to 40 ° C, and the pH was adjusted to 9-10 with a 10% aqueous NaOH solution, and filtered to remove possible insoluble impurities. The salt was added in an amount of 200 g of sodium chloride per liter of the reaction volume, and the solid was washed with a 20% sodium chloride solution, and then washed with a small amount of water to obtain 50 g of a black compound (13).

The obtained compound (13) was separated into three main product peaks by high performance liquid chromatography, and separated by HPLC:

Compound 13-1: a = l, b = l, c = 0;

Compound 13-2: a = l, b = l, c = l;

Compound 13-3: a = 2, b = l, c = l;

Electrospray ionization mass spectrometry showed that the m/z peak of compound 13-1 in negative mode was: 409.3 (base peak, [M-3Na]/3), 614.5 ([M+H-3Na]/2), all proved to be dye The molar mass M of the molecule was 1297.0, which was in agreement with the theoretical value. The m/z peak of compound 13-2 is: 365.5 [(M-4Na)/4], 487.67 [(M-4Na+H)/3], 495.0 [(M-3Na)/3], 732.0 [(M -4Na+2H)/2], 743.0 [(M-3Na+H)/2], 754.0 [(M-2Na)/2], all proved that the molar mass M of the dye molecule was 1554.0, which was in agreement with the theoretical value. The m/z peak of compound 13-3 is: 385.4 [(M-5Na+H)/4], 390.9 [(M-4Na)/4], 514.3 [(M-5Na+2H)/3], 521.6 [ (M-4Na+H)/3], 529.0 [(M-3Na)/3], both proved that the molar mass M of the dye molecule was 1655.9, which was in agreement with the theoretical value. Example 9

Synthesis of Compound (14)

90 parts of cyanuric chloride (36 parts) and sodium 2-amino-3,6,8-trinaphthalene sulfonate were added to 800 parts of water, reacted for 5 hours under stirring of 0-5, and an aqueous solution of NaHCO _{3 was} added dropwise to control the reaction. The pH of the system is between 8-9. Then, it was further reacted at room temperature for 1 hour. Ethylenediamine (12 parts) was added, the temperature was raised to 40-45 ° C, and the aqueous solution of NaHCO _{3 was} added dropwise to control the pH of the reaction system at 8-9, and the reaction was stirred at this temperature for 5 hours. Then, the mixture was cooled to 30 ° C, the above chlorosulfonated filter cake was added, 1000 parts of ice water was added, and the reaction was stirred at 40-45 ° C, while 10% aqueous NaOH solution was added dropwise to control the pH of the reaction system at 8-9, and stirred for 3 hours. , gradually increase the temperature and react at 50-55 ° C for 1 hour. Finally, it was cooled to 40 ° C, and the pH was adjusted to 9-10 with a 10% aqueous NaOH solution, and filtered to remove possible insoluble impurities. The salt was added in an amount of 200 g of sodium chloride per liter of the reaction volume, and the solid was washed with a 20% sodium chloride solution, and then washed with a small amount of water to obtain a black compound (14) 70 parts of the obtained compound (14). Separated into three main product peaks, separated by HPLC preparation:

Compound 14-1: a = l, b = l;

Compound 14-2: a = 2, b = l;

Compound 14-3: a = l, b = 2 _;

Compound 14-4: a = 3, b = l;

Electrospray ionization mass spectrometry (API-ES) detection, in negative mode, the m/z peak of compound 14-1 is: 339.2 [(M-4Na)/4], 452.6 [(M-4Na+H)/3] It is proved that the molar mass M of the dye molecule is 1449.0, which is in agreement with the theoretical value.

The m/z peak of compound 14-2 is: 359.2 [(M-5Na+H)/4], 364.7 [(M - 4Na)/4], 479.3 [(M-5Na+2H)/3], 486.6 [ (M-4Na+H)/3], 719.4[(M-5Na+3H)/2, 730. 4[(M-4Na+2H)/2], 741.4 [(M-3Na+H)/2] It is proved that the molar mass M of the dye molecule is 1550.9, which is in agreement with the theoretical value.

The m/z peaks for compound 14-3 are: 498.2, 498.7, 499.2 [(M-6Na+2H)/4], 503.7, 504.2, 504.7 [(M-5Na+H)/4], 664.6, 665.2, 665.9 [(M-6Na+3H)/3] , 671.9, 672.6, 673.2 [(M-5Na+2H)/3], 679.3, 679.9, 680.6 [(M-4Na+H)/3], 1019.4, 1019.9, 1021.4 [(M-4Na+2H)/2], both proved that the molar mass M of the dye molecules was 2128.8, 2130.8, 2132.8 (isotopes;), which was in agreement with the theoretical value. The m/z peak of compound 10-4 has: 528.0 (base peak, [M-3Na]/3), 390.2 ([M-4Na]/4), 792.4 C [M-3Na+H]/2), It is proved that the molar mass M of the dye molecule is 1652.9, which is a kiss with the theoretical value.

Ink Example 10

The present invention uses an EPSON RX690 inkjet integrated machine to separately print self-contained black ink on Epson photo paper and inkjet paper to form images and characters.

Preferred ink formula is as follows

Dye (direct black 19 ) 10g

Water (50 ° C) 20ml

Ethylene glycol 5ml

Diethylene glycol 3ml

Ethanol 2ml

2-pyrrolidone 3ml

Diethylene glycol monobutyl ether 5ml

20% NP-10 (surfactant) 0.1ml

Preservative Proxel GXL 0.5g

Adjust pH=8.0, add water to the total volume of 100ml after cooling, stir well and filter with 0.2μηι pore size filter.

The dye direct black 19 in the above Example 10 of the ink was replaced with the dye compound 2-14 to obtain dye inks 1-13, respectively. Performance testing and evaluation

The present invention is a color block formed by printing the black ink prepared above on Epson photo paper and Epson ink jet paper by a commercially available special ink jet printer, and performing the following four performance tests and evaluations. A: Light resistance performance test; B anti-ozone performance test; C water fastness test; D storage stability test.

A: Lightfastness test: Put a sample of paper with printed color blocks into an accelerated test device that provides high-intensity ultraviolet light by using a xenon lamp as an ultraviolet light source. After 18 hours of high-intensity exposure test, test the color density (OD) of the sample before and after illumination. Value, and the color density retention rate OD _a % was obtained from the following formula.

OD _a %= OD after illumination / OD before illumination χ 100%

Evaluation criteria: OD _a value between 80 - 100; ◎

00&value is between 70 and 80; o 00&value is between 50 and 70; △

OD _a value is less than 50; χ

B: Anti-Ozone Performance Test: A sample of the paper on which the colored block was printed was placed in an accelerated test apparatus having an ozone concentration of 1 ppm, and the OD value of the sample was measured after 18 hours, and the color density retention rate OD _a % was obtained from the following formula.

OD _b %= OD after illumination / OD before illumination χ 100%

Evaluation criteria: OD _b value between 80 - 100; ◎

001 ₅ values between 70 and 80; o

OD _b value between 50 - 70; △

OD _b value is less than 50; X

C: Water fastness test: Print inkjet ink on Epson inkjet paper, 50. C, Under the condition of 85% humidity, leave it for one week and visually change the image of the patch before and after.

Evaluation criteria: No change in color patch image; ◎

There is a small penetration between the patch images; o

Most of the infiltration between the patch images; Δ

Complete penetration between color block images; X

D: Storage stability test: Place the prepared inkjet ink at 40 ° C for one month, and visually check for the presence of insoluble matter.

Evaluation criteria: no suspended matter; o

Suspended matter appears; △

Insoluble matter appears; X

The performance evaluation is shown in Table 1 below.

7 8 ◎ ◎ ◎ 〇

8 9 ◎ ◎ ◎ 〇

9 10 ◎ ◎ ◎ 〇

0 11 ◎ ◎ ◎ 〇

11 12 ◎ ◎ ◎ 〇

12 13 ◎ ◎ ◎ 〇

13 14 ◎ ◎ ◎ 〇

10 direct black 19

X X ◎ 〇

As can be seen from Table 1, the inkjet ink containing the black dye of the present invention has excellent storage stability and water fastness, and has excellent light resistance as compared with the inkjet ink of the mainstream black dye currently on the market. And ozone resistance.

For the sake of convenience of operation, the dyes (Compounds 2-14) used in the inks 1-13 used in Table 1 were directly mixed with the dye compounds synthesized in the respective examples, and the mixture was not separated into individual compounds. Directly formulated with ink. For example, the dye of Ink 1 is a mixture of Compounds 2-1, 2-2 and 2-3, and the dye of Ink 13 is a mixture of Compounds 14-1, 14-2, 14-3 and 14-4, and the like.

Further, the applicant also separates the compound mixture synthesized in each of the examples by a conventional separation method, and then separates the separated pure compound into an ink, and respectively tests. The properties of inks formulated with pure compounds, including lightfastness, ozone resistance, water fastness and storage stability, were found to be the same as the corresponding inks formulated with the mixture. Specifically, the inks prepared by using the compounds 14-1, 14-2, 14-3, and 14-4, respectively, and the ink compound (i.e., ink 13) formulated with the dye compound mixed therewith have light resistance and ozone resistance. Sex and water fastness and storage stability are the same. The same is true for the other dye inks.

Claims

Rights request

A weatherable black dye comprising a compound of the formula (I) or a mixture thereof:

-CH ₂ CH ₂ NH— (\ N Re

B

R ₅ and R _{6 in} B may be the same or different and are selected from the group consisting of: F, Cl, Br, OH, NH ₂ , NHCN, N(CH ₃ ) ₂ , NHCONH ₂ , NH(CR ₃ R4) „A, N(( CR ₃ R4) „A) ₂ , NR ₃ A ₂ , SH, or S(CR ₃ R4) „A;

A ₂ is a phenyl or naphthyl group having 1-5 substituents A ₃ ; A _{3 is} selected from the group consisting of H, Cl, Br, CN, CF ₃ , CH ₃ , NO ₂ , NH ₂ , SO ₃ M, CO ₂ M,,, PO ₃ M,, ₂ , or PO ₃ HM,,;

2. A dye according to claim 1, wherein said M, and M "are each independently H, Na, K, Li, NH 4, N (CH 3) 4, NH (CH 3) 3, NH ₂ (CH ₃ ) ₂ , NH ₃ (CH ₃ ) ₄ , NH(CH ₂ CH ₂ OH) ₃ , NH ₂ (CH ₂ CH ₂ OH) ₂ or NH ₃ CH ₂ CH ₂ OH.

3. The dye of claim 1 wherein said a+b is 2-4.

4. The dye according to claim 1, wherein the sum and R ₂ are the same or different from H,

The base of Ci_4.

5. A method of preparing a black dye compound of the general formula (I), which comprises:

The compound (Io) is first synthesized by the following multi-step reaction process:

Compound (1 ₀ ) Then, the compound (I _Q ) is further reacted with chlorosulfonic acid and a chlorinating reagent to obtain a structural formula (II); then, the active acyl chloride group in the formed compound of the formula (Π) is subjected to alkaline hydrolysis. Obtaining a dye compound of the formula (I), or a compound of the formula (Π) with an aqueous ammonia or an amine compound, and then neutralizing with a base to obtain a dye compound of the formula (I); X in the formula (II) is not Less than 2;

(II)

6. A method of preparing a black dye compound of the formula (I) wherein b is 0, which comprises:

Compound (iota ₀₎ Then, the compound (I _Q) is reacted with sulfuric acid to give the general structural formula (111), and then a base, to give a compound of formula b is 0, a dye (I),; Y is not less than 2;

(III)

7. The method according to claim 5, wherein the molar ratio of the chlorosulfonic acid to the compound (I _Q ) is from 20 to 2000:1, and the molar ratio of the chlorinating reagent to the compound (I _Q ) is from 2 to 500. : 1, the reaction temperature is between 50 - 250 °C.

8. The method according to claim 6, wherein the molar ratio of the sulfuric acid to the compound (I _Q ) is

5-6000:1, reaction temperature is 20-250 °Co

9. An aqueous inkjet ink composition comprising: 1-20% by weight of the dye of claim 1, 5-50% by weight of a water-miscible organic solvent, and 30-94% by weight of water, in combination The total weight of the object is the basis.

10. Use of a dye according to claim 1 for use as a colorant in the following materials: inks, coatings, lacquers, laser-printed toners, markers, paper, fabrics, glass, ceramics, or polymers.