WO2010075783A1

WO2010075783A1 - Weatherable perylene imide dye, thereof preparation and use

Info

Publication number: WO2010075783A1
Application number: PCT/CN2009/076229
Authority: WO
Inventors: 彭孝军; 邹德新; 王静月; 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

Water-soluble perylenetetracarboxylic acid bisimide dyes of formula (I), thereof preparation and use, wherein R₁and R₂are independently H or water-soluble group connecting on the naphthalene ring，R₃、R₄、R₅ and R₆ are independently selected from neutral substituting group or water-soluble group, n and m are both integer of not less than 2. The perylenetetracarboxylic acid bisimide dyes of formula (I) can be used for colorant of ink, coating, painting, toner of laser pinter, marker, paper, textile, glass, ceramic or polymer.

Description

Weather-resistant phthalimide dye, preparation method and use thereof

Technical field

The present invention relates to a weather-resistant phthalimide dye, a preparation method and use thereof, and more particularly to a novel weather-resistant bismuth carboxylic acid bisdiimide dye derivative, a synthesis method thereof and use thereof. Background technique

Terpene tetracarboxylic acid bisdiimide, also known as perylene diimide, has good thermal stability, chemical stability, and photochemical and photophysical stability. When used as dyes and pigments, they are widely used in photoengraving processes, laser dyes, solar cell materials, liquid crystal materials, organic field effect transistors, luminescent materials, and the like.

In recent years, with the development of inkjet printing technology and the ever-expanding range of applications, the quality requirements for inkjet printing drawings are getting higher and higher. For inkjet prints used in harsh climates, it is generally required to have excellent weather resistance, namely good resistance to ultraviolet (UV), ozone (0 ₃ ), acid and alkali resistant gases and fine dust particles. In view of the excellent anti-UV and anti-O ₃ ability of some phthalimide dyes, the research on its application in the field of inkjet printing has been gradually developed in recent years, but no commercially available phthalimide dye products have been available. . Summary of the invention

It is an object of the present invention to provide a novel weatherable phthalimide dye compound and a process for the preparation thereof. In a first aspect of the invention, the structure of a weatherable phthalimide dye compound is as defined in formula (I):

Wherein: the naphthalene ring structure is directly bonded to the nitrogen atom of the diimide by a tertiary carbon atom; ^ and independently of each other, H or a water-soluble group attached to the naphthalene ring; R ₃ , R ₅ and independently of each other It is selected from a neutral substituent or a water-soluble group; n and m are each a number, and n and m are integers not less than 2.

In a preferred embodiment of the dye compound, the naphthalene ring structure passes through a tertiary carbon atom at the 2-position on the naphthalene ring. Directly bonded to the nitrogen atom of the diimide.

In another preferred embodiment of the dye compound, ! And independently of each other, a water-soluble group attached to the naphthalene ring except for the 2 position. 1 and preferably each are H, SO ₃ H or SO ₃ M.

The water-soluble group in the dye compound of the present invention is preferably selected from the group consisting of: SO ₃ H, COOH, SO ₃ M or COOM, wherein M is a cation, and M is selected from the group consisting of: Li ⁺ , Na ⁺ , K ⁺ , imidazolium cation or N ⁺ ( R) ₄ , wherein R is H, CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH(CH ₃ ) or CH ₂ CH ₂ CH ₂ CH ₃ . More preferably, SO ₃ H or SO ₃ M.

The neutral substituent in the dye compound of the invention is preferably selected from the group consisting of: H, cyano or a halogen atom.

In still another preferred embodiment of the dye compound of the invention, n+m 5 .

In still another preferred embodiment of the dye compound of the present invention, when two or more water-soluble groups are present on each naphthalene ring, they are not in an adjacent position on the naphthalene ring.

In still another preferred embodiment of the dye compound of the present invention, at least one of R, R ₅ and R 6 is a H atom, more preferably at least two are H atoms, more preferably all H atoms.

In a second aspect of the invention, a method of preparing a phthalimide dye compound of formula (I), comprising the steps of:

(a) First introducing a neutral or water-soluble group R ₃ , , and 1^ into a perylenetetracarboxylic dianhydride of the formula (Π):

A substituted ruthenium tetracarboxylic dianhydride compound of the formula (m) is obtained:

(m)

(b) Substituting the substituted tetracarboxylic dianhydride of formula (m) with the amino group of formula (IV)

The sulfonic acid compound is reacted under the following reaction conditions:

(IV) The reaction is carried out in the presence of the catalyst Zn(C3⁄4COO) ₂ · 2Η ₂ 、 under an inert gas in an organic solvent; the substituted fluorene tetracarboxylic dianhydride of the formula (ΠΙ), the amino group of the formula (IV) The molar ratio of the sulfonic acid compound, the catalyst, and the organic solvent is 1:3-10: 0.55~0.94:6~20, and the organic solvent is selected from one or more of imidazole, N-methylpyrrolidone or quinoline, reaction temperature 100-240 ° C, the reaction time is 1-12 hours;

The product obtained by the reaction is dissolved in water, filtered, and precipitated, and finally filtered to give a solid compound of the formula (I). In a preferred embodiment of the process of the invention, before the start of the reaction, the catalyst comprises

Substituting 茈tetracarboxylic dianhydride of (m), a solid reaction mixture of a reaction material of the amino polysulfonic acid compound of the formula (no) and a solid solvent at a temperature lower than the reaction temperature while stirring to change the solid reaction mixture In a liquid state, the reaction is then carried out by raising the temperature to 100-240 °C.

In the process of the present invention, the reaction temperature is preferably from 120 to 220, more preferably from 150 to 220 ° C, still more preferably from 160 to 200.

V.

In another preferred embodiment of the process of the present invention, water is separated while the reaction is carried out, and the solvent is distilled off together with the water formed in the reaction by distillation to increase the yield.

In still another preferred embodiment of the method of the present invention, the inert gas is nitrogen or argon. In a third aspect of the invention, 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 fourth aspect of the invention, the invention relates to an inkjet aqueous ink composition comprising: 1-20% by weight of the above dye compound, 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 fifth aspect of the invention, there is provided a coating comprising the above dye compound of the invention. The coating is preferably an outdoor coating. In a sixth aspect of the invention, there is provided a lacquer comprising the above dye compound of the invention. The lacquer is preferably an outdoor lacquer.

In a seventh aspect of the invention, a toner for laser printing comprising the above dye of the invention.

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

In a ninth 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 a tenth 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. DRAWINGS

Figure 1 is a high performance liquid chromatogram of the dye compound prepared in the examples. detailed description

In the dye compound of the formula (I) of the present invention, the naphthalene ring structure is directly bonded to the nitrogen atom of the diimide via a tertiary carbon atom, preferably directly to the nitrogen of the diimide via a tertiary carbon atom at the 2-position on the naphthalene ring. Atomic bonding.

1 and independently of each other are water-soluble groups or H atoms attached to the naphthalene ring, wherein the water-soluble group is preferably SO ₃ H or SO ₃ M, which group imparts good water solubility to the dye compound. 1 and preferably, independently of each other, are water-soluble groups attached to the naphthalene ring except for the 2 position.

n and m represent the number of 1^ and on the naphthalene ring, respectively, preferably 2, more preferably 3. n+m 5, more preferably 6.

In the present invention, the water-soluble group is preferably selected from the group consisting of: SO ₃ H, COOH, SO ₃ M or COOM, wherein M is a cation, and M is selected from the group consisting of: Li ⁺ , Na ⁺ , K ⁺ , imidazolium cation or N ⁺ (R) ₄ , wherein M is more preferably selected from the group consisting of: Li ⁺ , Na ⁺ , K ⁺ , imidazolium cations.

R _3⁄4 Η, CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH(CH ₃ ) or CH ₂ CH ₂ CH ₂ CH ₃ , R is more preferably H, CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ .

In the dye compound of the present invention, when two or more water-soluble groups are present on each naphthalene ring, they are not in an adjacent position on the naphthalene ring.

R ₃ , R ₅ and independently of each other are H, a neutral substituent or a water-soluble group. Among them, a water-soluble group is also preferably SO ₃ H or SO ₃ M, which group imparts good water solubility to the dye compound. The neutral substituent is preferably a halogen atom or a cyano group, more preferably a halogen atom, and includes a chlorine atom, a bromine atom, and an atomic iodine. , Preferably, at least one of , and 1 is a H atom, and more preferably two are H atoms. In the method for producing a weatherable phthalimide dye compound of the present invention, the following steps are included:

(a) First, a neutral substituent or a water-soluble group R ₃ , , and 1^ are introduced into a perylenetetracarboxylic dianhydride of the formula (Π) to obtain a substituted indole tetracarboxylic dianhydride compound of the formula (ΠΙ).

(II) (III)

The manner in which the neutral substituent or the water-soluble group R ₃ , and the perylenetetracarboxylic dianhydride of the structural formula (Π) are introduced can be halogenated by halogen, and halogen can be introduced by a method known in the art. Atomic substituent; sulfonation with fuming sulfuric acid, introduction of a sulfonic acid substituent, halogenation with a halogen followed by cyanation with sodium cyanide, potassium cyanide or cuprous cyanide, introduction of a cyano substituent, etc. Wait. These methods are described in many documents, for example, J. Org. Chem. 2004, No. 69, pp. 7933-7939; and Zhurnal Organicheskoi Khimi, 1992, Vol. 28, No. 7, pp. 1486-1488.

Specific examples of the halogenated phosphotetracarboxylic dianhydride compound obtained in the step (a) include: 1, 7-dichloroindole tetracarboxylic dianhydride, 1,6,7-trichloroindole tetracarboxylic dianhydride, 1, 6, 7, 12-tetrachloroanthracene tetracarboxylic dianhydride, 1,7-dibromofluorene tetracarboxylic dianhydride, 1,6,7-tribromofluorene tetracarboxylic dianhydride, 1, 6, 7 , 12-tetrabromofluorene tetracarboxylic dianhydride, 1,7-diiodofluorene tetracarboxylic dianhydride, 1,6,7-triiodofluorene tetracarboxylic dianhydride, 1, 6, 7, 12-tetraiodide One or more mixtures of tetracarboxylic dianhydrides.

Specific examples of the sulfonic acid-substituted perylenetetracarboxylic dianhydride compound include: 1, 7-disulfonic acid ruthenium tetracarboxylic dianhydride,

One or more of 1, 6, 7-trisulphonic acid tetracarboxylic dianhydride, 1,6,7,12-tetrasulfonic acid ruthenium tetracarboxylic dianhydride.

(b) a substituted indole tetracarboxylic dianhydride compound obtained in the step (a), an aminopolysulfonic acid compound of the formula (IV), a catalyst, and an organic solvent molar ratio 1: 3-10: 0.55 to 0.94:6 ～20 is mixed together, the catalyst is Zn(CH ₃ COO) ₂ · 2Η ₂ Ο, and the organic solvent is selected from one or more of imidazole, fluorene-methylpyrrolidone, and quinoline. Under the protection of an inert gas, the temperature of the reaction system is raised to 100-240 ° C, and the reaction is started, and the reaction time is 1 to 12 hours. Then, the product obtained by the reaction is dissolved in water, filtered, and precipitated, and finally filtered to obtain a solid compound of the formula (I).

The final treatment of the reaction product described in step (b), including water dissolution, filtration, precipitation, and finally Filtration, etc., are all procedures well known in the industry. In a preferred embodiment, the product is dissolved in water, filtered, and then the filtrate is dropped into an organic solvent to precipitate the product, filtered, and the solid is washed several times with an organic solvent to obtain a compound of the formula (I).

In the process for the preparation of the compound of the formula (I) of the present invention, the aminopolysulfonic acid compound of the formula (IV) used may be, for example, 2-amino-3,6-naphthalenetrisulfonic acid or 2-amino-4. One or two of 6, 8-naphthalenetrisulfonic acid, or one of 2-amino-3,6-naphthalenetrisulfonic acid, 2-amino-4,6-naphthalenetrisulfonic acid , and 2-amino 4-naphthalene disulfonic acid, 2-amino-1, 5-naphthalene disulfonic acid, 2-amino-1,6-naphthalenedisulfonic acid, 2-amino-1,7-naphthalene disulfonate Acid, 2-amino-1, 8-naphthalene disulfonic acid, 2-amino-3, 5-naphthalenedisulfonic acid, 2-amino-3,6-naphthalene disulfonic acid, 2-amino-3, 7-naphthalene Disulfonic acid, 2-amino-3, 8-naphthalenedisulfonic acid, 2-amino-4,6-naphthalene disulfonic acid, 2-amino-4,7-naphthalene disulfonic acid, 2-amino-4, 8 One or more of naphthalenedisulfonic acid, 2-amino-5,7-naphthalene disulfonic acid, 2-amino-5, 8-naphthalene disulfonic acid, 2-amino-6, 8-naphthalene disulfonic acid a mixture of components.

In this step of the process of the present invention, it is preferred to carry out preheating while stirring before the start of the reaction, in order to convert the solid reaction mixture into a liquid state to facilitate the progress of the reaction, and the preheating is also carried out under the protection of an inert gas. The heating temperature is lower than the reaction temperature. It is preferably 80-100 ° C, more preferably 90-100 ° C, and the preheating time is preferably 0.5-1 hour.

After the solid reaction mixture became a liquid, the temperature was raised to 100-240 ° C to carry out the reaction.

In the process of the present invention, the reaction temperature is preferably from 120 to 220, more preferably from 150 to 220 ° C, still more preferably from 160 to 200 V. When the reaction temperature is high, the reaction time can be shortened accordingly.

In the method of the present invention, it is preferred to carry out water separation while the reaction is carried out, gp: by distillation, the solvent in the reaction system is distilled out together with the water formed in the reaction, thereby increasing the yield of the product. .

In the process of the invention, the inert gas used is preferably nitrogen or argon, more preferably nitrogen.

The yield of the target product obtained by the process of the invention after separation and purification is above 70%. The obtained compound was confirmed by high performance liquid chromatography-mass spectrometry (HPLC-MS) and the structure was correct.

The main principle of the invention is as follows: the large conjugated electron-deficient system in the dye structure is used as a matrix to reduce the HOMO energy level of the excited state of the dye molecule, and the high-energy electrons in the molecular excited state after the dye is excited are transferred in time to improve The dye is resistant to UV and ozone, and at the same time, a water-soluble group and a halogen substituent are introduced into the dye molecule, so that the dye has excellent water solubility, weather resistance, light resistance and ozone resistance.

The HOMO energy levels for dye or organic compound molecules are well described in many monographs or literature, as published by CJ Cramer, Essentials of Computational Chemistry, John Wiley & Sons, Inc., 2002. After an organic molecule such as a dye absorbs light of a suitable wavelength, an electron at the HOMO level in the dye molecule gains energy and transitions to the LUMO (lowest non-occupied orbital) level. The dye molecules are excited and activated. At this time, the dye molecules are highly susceptible to decomposition reactions or chemical reactions with other molecules such as oxygen (or ozone) to destroy and discolor the original molecules. If an electron donor group is present in the dye molecule at this point, an electron in the HOMO level of the donor group will shift to the HOMO level of the vacant dye precursor molecule. This process is often referred to as electron transfer. Since electron transfer in the molecule is much faster than electron transfer between molecules, the introduction of an electron donor group into the molecule allows electron transfer to occur rapidly, called photoinduced intramolecular electron transfer (PET).

On the other hand, if there is an electron acceptor with a very low energy level in the molecule, the excited electrons will quickly fall back into the electron acceptor, that is, the electrons fall back from the LUMO level of the dye to the HOMO level of the electron acceptor, so that the dye The molecular excitons are rapidly quenched. This is a process opposite to the above-described electron transfer direction, called anti-PET. Based on this, the inventors have completed the present invention.

The advantages of the dye compounds of the invention are:

1. The dye compound has strong UV absorption at 530~550nm, which is a blue red dye.

2. The dye compound is simple in synthesis and has excellent water solubility.

3. The dye compound has excellent UV and O ₃ resistance, and the formulated ink has

The cost is low, the weathering performance of the printed picture is excellent, and the ink of the same type of foreign original is close to or exceeds in the anti-UV and anti-O ₃ performance.

The dye of the present invention can form a vivid color. It is a red dye and is one of the traditional three primary colors. It can be used in combination with other types of red dyes, and can also be combined with dyes of other colors to form various desired colors.

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 ink, coating ink, or inkjet ink, 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 is in the storage period before application, even in the air. Gases (such as oxygen and nitrogen) are in contact with light and also have long-term color stability and are not easily faded. 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. 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 long-term color stability and is not easily faded even during contact with gases and light in the air during storage prior to use. After the ink is jet printed onto the medium, the resulting image also has long-term color stability.

The synthesis of the dye compound of the present invention and its weather resistance, such as solar and ozone resistance, are illustrated by the following examples, but are not limited to the examples.

Example

Example 1

Preparation of Compound (V) (Μ is Η ⁺ or imidazolium cation):

(V)

Lg (2.5 mmol) of ruthenium tetracarboxylic dianhydride (99.8%) and 4.1 g (7.5 mmol) of 2-amino-3,6-naphthalenetrisulfonic acid (70%), 0.35 g (1.8 mmol) of Zn ( CH ₃ COO) ₂ · 2H ₂ O, imidazole llg is uniformly mixed, heated to 90~100 ° C under nitrogen protection, the solid is dissolved into a viscous state, stirred for 0.5 h, heated to 150~180 V, separated water , the reaction is 1~2h, the red slurry is obtained, the reaction is stopped, the reactant is poured into 15~20ml of water, fully dissolved by stirring, the solid impurities are filtered off, and the filtrate is concentrated if necessary, and 150 ml of ethanol is added dropwise to the filtrate until solid The solid was washed with ethanol under reflux for 2 to 3 times to give a dark red solid, which was dried and weighed to give a solid.

The maximum absorption wavelength max of the ultraviolet visible spectrum in the dye aqueous solution is 498 nm and 535 nm, and the salt form of the partial -SO ₃ M in the dye molecule is different, and the obtained high performance liquid chromatogram (HPLC) shows two peaks. M The molar mass of the compound (V) should be 1123.0 in terms of H ⁺ . Electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray ionization mass spectrometry has a base peak with a mass-to-charge ratio of 560.5, which is the di-negative ion peak of the dye (molecular mass [MW-2H]/2), and has a mass charge. The negative ion peak of 570.8 ([MW-3H+Na]/2) has a mass-to-charge ratio of 373.1, 747.6, 754.5 three negative ion peaks ([M-3H]/3, [2M-3H/3], respectively [ 2M-4H+Na]/3), an anion peak ([MH]) with a mass-to-charge ratio of 1121.7, all proved that the molar mass of the dye molecule was 1123, which was in agreement with the theoretical value. At the same time, a small amount of dye molecules with a naphthalene ring unilaterally linked to the naphthalene ring was also found. M is calculated as H ⁺ , and the molecular molar mass of the dye molecule should be 757.7. In the negative mode, electrospray mass spectrometry has a peak of mass ratio of 756.4. Is an anion peak ([MH]) of the dye molecule. The liquid chromatogram is shown in Figure 1 (measured by a mixed solvent of methanol and water), wherein the peaks 10.573 and 14.849 are dye molecules of the anthracene ring bilaterally linked to the naphthalene ring, and M is an imidazolium cation and a tetramethylammonium of a reversed phase ion pair. The cation, peak 24.363 is a dye intermediate molecule which is unilaterally bonded to the naphthalene ring. Example 2

Preparation of Compound (VI) (M is H+ or imidazolium cation):

(VI) The 2-naphthalene-3,6-trisulphonic acid of Example 1 was replaced with 2-naphthalene-4,6-trisulphonic acid (7.5 mmol) to obtain the compound (VI), which was dried. Solid 2.3 g.

The maximum absorption wavelength max of the ultraviolet visible spectrum in the aqueous dye solution is 499 nm and 534 nm, and the salt form of the partial -SO ₃ M in the dye molecule is different, and the obtained high performance liquid chromatogram (HPLC) shows two peaks. M has a molecular molar mass of 1123 in terms of H ⁺ and the compound (VI). Electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray ionization mass spectrometry has a base-to-charge ratio of 560.5, which is the di-negative ion peak of the dye (molecular mass [MW-2H]/2), and has a mass-to-charge ratio. The negative ion peak of 570.8 ([MW-3H+Na]/2), the mass-to-charge ratio is 373.1, 747.6, 754.5 three negative ion peaks ([M-3H]/3, [2M-3H/3], [2M, respectively] -4H+Na]/3), an anion peak ([MH]) with a mass-to-charge ratio of 1121.7, all proved that the molar mass of the dye molecule was 1123, which was in agreement with the theoretical value. At the same time, a small amount of dye molecules with a naphthalene ring unilaterally linked to the naphthalene ring was also found. M is calculated as H ⁺ , and the molecular molar mass of the dye molecule should be 757.7. In the negative mode, electrospray mass spectrometry has a peak of mass ratio of 756.4. Is an anion peak ([MH]) of the dye molecule. Example 3

Preparation of compound ( ) (Μ is an imidazolium cation):

The compound (V) prepared in lg Example 1 was dissolved in a mixed solution of 5 g of imidazole and 5 ml of water, and heated to 60 ° C for 30 min. After cooling, ethanol was added dropwise to the solution to precipitate a solid, which was filtered and washed with ethanol. The solid was 2-3 times and dried to give a solid 1.2 g.

The maximum absorption wavelength max of the ultraviolet visible spectrum in the dye aqueous solution was 498 nm and 535 nm, and the obtained high performance liquid chromatogram (HPLC) showed a peak. M is based on the imidazolium cation and the molecular molar mass of the compound should be 1537. Electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray ionization mass spectrometry has a base-to-charge ratio of 186.2, which is the six negative ion peak of the dye (molecular mass [MW-6M _ΡΒ ]] / 6), proof The molar mass of the dye molecule is 1537, and the dye is indeed ruthenium, iridium-bis(2-naphthalene-3,6-trisulphonate imidazolium salt) ruthenium tetracarboxylic acid diimide, in line with the theory. Example 4

Preparation of compound (Europe):

(1) The compound (V) prepared in lg Example 1 was dissolved in 5 ml of water to prepare an aqueous solution, and concentrated HC1 was added dropwise to adjust the pH to a solid. The mixture was heated to 60 ° C and stirred for 30 min. The solid was dissolved in 5 ml of water, and the pH was adjusted to 8 to 9 with a 1 mol/L NaOH solution. Ethanol was added dropwise to the aqueous solution to precipitate a solid, which was filtered and washed with ethanol for 2 to 3 times, and dried to give a solid. The maximum absorption wavelength max of the ultraviolet visible spectrum in the aqueous dye solution was 497 nm and 536 nm, and the obtained high performance liquid chromatogram (HPLC) showed a single peak. M is in terms of Na ⁺ and the molecular molar mass of the compound should be 1253. Electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray mass spectrometry has a base-to-charge ratio of 185.3, which is the six negative ion peak of the dye (molecular mass [MW-6M _Na ⁺ ]/6), which proves that the dye is indeed It is Ν, Ν-bis(2-naphthalene-3,6,8-trisulphonate sodium salt) ruthenium tetracarboxylic acid diimide, in line with the theory. Example 5

Compound (Preparation of DO (M is N+ (CH ₃ ) ₄ ):

(DO

The compound (V) prepared in lg of Example 1 was dissolved in 5 ml of water to prepare an aqueous solution, and concentrated HC1 was added dropwise to adjust the pH to a solid. The mixture was heated to 60 ° C and stirred for 30 min. The solid was dissolved in 5 ml of water, and the pH was adjusted to 8 to 9 with a 5% solution of (CH ₃ ) ₄ Ν · 0 ,. Ethanol was added dropwise to the aqueous solution to precipitate a solid, which was filtered and washed with ethanol for 2 to 3 times and dried. The solid was 0.85 g. The maximum absorption wavelength max of the ultraviolet visible spectrum in the dye aqueous solution was 499 nm and 535 nm, and the obtained high performance liquid chromatogram (HPLC) showed a single peak. M The molar mass of the compound should be 1,560 based on N ⁺ (CH ₃ ) 4 . Electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray ionization mass spectrometry has a base-to-charge ratio of 185.3, which is the six negative ion peak of the dye (molecular mass [MW-6M _N ⁺ ( _CH3 ) 4]/6 ), it is proved that the dye is indeed ruthenium, iridium-bis(2-naphthalene-3,6-trisulphonic acid tetramethylamine salt) ruthenium tetracarboxylic acid diimide, in line with the theory.

Example 6

Preparation of Compound (X) (Μ is Η+ or imidazolium cation):

(X) The perylenetetracarboxylic dianhydride of Example 1 was replaced with 1,7-dibromofluorene tetracarboxylic dianhydride (2.5 mmol) to obtain a compound (X), which was dried to give a solid (2.5 g).

The maximum absorption wavelength max of the ultraviolet visible spectrum in the aqueous dye solution is 501 nm and 534 nm, and the salt form of the partial -SO ₃ M in the dye molecule is different, and the obtained high performance liquid chromatogram (HPLC) shows two peaks. M The molar mass of the compound (V) should be 1280.8 in terms of H ⁺ . Electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray ionization mass spectrometry has a base-to-charge ratio of 639.4, which is the di-negative ion peak of the dye (molecular mass [MW-2H]/2), and has a mass-to-charge ratio. The negative ion peak of 650.6 ([MW-3H+Na]/2), the mass-to-charge ratio is 425.9, 852.8, 860.4 three negative ion peaks ([M-3H]/3, [2M-3H/3], [2M, respectively) -4H+Na]/3), an anion peak ([MH]) with a mass-to-charge ratio of 1280.0, all proved that the molar mass of the dye molecule was 1280.8, which is in agreement with the theoretical value. At the same time, a small amount of dye molecules with a naphthalene ring unilaterally linked to the naphthalene ring were also found. M has a molecular molar mass of 915.5 in terms of H ⁺ , and in negative mode, electrospray mass spectrometry has a peak with a mass-to-charge ratio of 914.4. Is an anion peak ([MH]) of the dye molecule. Example 7

Preparation of Compound (XI) (M is H ⁺ or imidazolium cation):

(XI) The perylenetetracarboxylic dianhydride of Example 1 was replaced with 1,7-dicyanoindoletetracarboxylic dianhydride (2.5 mmol) to obtain Compound (XI), which was dried to give a solid (2.3 g).

The maximum absorption wavelength max of the ultraviolet visible spectrum in the aqueous dye solution is 503 nm and 536 nm, and the salt form of the partial -SO ₃ M in the dye molecule is different, and the obtained high performance liquid chromatogram (HPLC) shows two peaks. M The molar mass of the compound (; V) should be 1173.0 based on H ⁺ . Electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray ionization mass spectrometry has a base-to-charge ratio of 585.5, which is the di-negative ion peak of the dye (molecular mass [MW-2H]/2), and has a mass charge. The ratio of the two negative ions of 596.7 ([MW-3H+Na]/2), the mass-to-charge ratio is 390, 78 788.5 three negative ion peaks ([M-3H]/3, [2M-3H/3], [2M, respectively] -4H+Na]/3), an anion peak ([MH]) with a mass-to-charge ratio of 1171.9.0, all proved that the molar mass of the dye molecule is 1173.0, which is in agreement with the theoretical value. At the same time, a small amount of dye molecules of the naphthalene ring unilaterally linked to the naphthalene ring were also found. M is calculated by H ⁺ , and the molecular weight of the dye molecule is The mass should be 807.7. In the negative mode, electrospray mass spectrometry has a peak with a mass-to-charge ratio of 806.5, which is an negative ion peak ([MH]) of the dye molecule. Example 8

Preparation of the compound (ΧΠ) (M is H+ or imidazolium cation):

The perylenetetracarboxylic dianhydride of Example 1 was changed to 1,7-disulfonic acid ruthenium tetracarboxylic dianhydride (2.5 mmol) to obtain a compound (ΧΠ), which was dried to obtain 2.4 g of a solid.

The maximum absorption wavelength max of the ultraviolet visible spectrum in the dye aqueous solution is 499 nm and 536 nm, and the salt formation form of the partial -SO ₃ M in the dye molecule is different, and the obtained high performance liquid chromatogram (HPLC) shows two peaks. M The molar mass of the compound (V) should be 1283.2 in terms of H ⁺ . Electrospray ionization mass spectrometry (API-ES) detection, in negative mode, electrospray ionization mass spectrometry has a base-to-charge ratio of 426.7, which is the three negative ion peak of the dye (molecular mass [MW-3H]/3), and has a mass charge. Compared with the negative ion peak of 651.8 ([MW-3H+Na]/2), the mass-to-charge ratio is 854.5, 862.0 three negative ion peaks ([2M-3H/3], [2M-4H+Na]/3, respectively). An anion peak ([MH]) with a mass-to-charge ratio of 1282.0 proved that the molar mass of the dye molecule was 1283.2, which was in agreement with the theoretical value. At the same time, a small amount of dye molecules with a naphthalene ring unilaterally linked to the naphthalene ring were also found. M has a molecular molar mass of 917.8 in terms of H ⁺ . In the negative mode, electrospray mass spectrometry has a peak with a mass-to-charge ratio of 916.5. Is an anion peak ([MH]) of the dye molecule. Example 9

Inkjet ink performance test and evaluation

Comparative dye hydrolysis CI active red 180:

(XIII) The dyes synthesized in Examples 1 to 8 and the commercially available commercial dyes, Hydrolyzed CI Reactive Red 180 (XIII), were each formulated into a red ink by the following formulation. The EPSON RX690 inkjet machine was used to print color blocks on Xerox paper, photo paper and inkjet paper, and the printed color blocks were tested for resistance to ultraviolet (UV) and ozone (0 ₃ ). The ink formula is as follows:

Dye 3g

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 a total volume of 100 ml after cooling, stir well and filter with 0.2μηι pore size filter to obtain inkjet ink. The dyes were the dyes synthesized in Examples 1 to 8, respectively, and the inks assigned thereto were respectively designated as inks 1 to 8, and the ink numbers obtained from commercially available commercial dyes C.I. Reactive Red 180 were inks 9. Color density value (OD value) of color block Test instrument and test method

The color density value of the color block is measured by a conventional color densitometer, such as the WI-QA-1011 color density meter purchased from Guangdong Zhongshan Rainbow Printing Consumables Co., Ltd. The measurement steps are as follows:

- Turn on the color density meter power switch for calibration.

- placing the test head on the unprinted portion of the paper to be measured for color density, measuring the parameters of the paper; Place the test head on the color block where the color density is to be measured, and the color density of the measured color block will be automatically displayed on the instrument screen. For a color patch, repeat the measurement several times at different locations and take the average.

UV resistance (UV) performance test method and evaluation criteria

A color block printed on different types of paper is placed in a UV-resistant accelerated test device that provides high-intensity ultraviolet light by using a xenon lamp as an ultraviolet light source. After a high-intensity ultraviolet light exposure test with a time T=24 hours, The OD value of each sample sample was tested, and the color density retention rate OD _a % of the sample after high-intensity exposure at the same time was calculated using the formula (6-1):

OD _a %=OD _T /OD ₀ X 100% (6- 1 )

Wherein, the OD _T is an OD value of the sample measured after the test of the length of time T;

OD. The initial OD value of the sample before it was tested

Evaluation criteria: OD _a value between 80 - 100; 〇

00; ₁ value between 70 - 80; 〇

OD _a value between 50 - 70; △

OD _a value is less than 50; X ozone resistance (0 ₃ ) performance test method and evaluation standard

The color blocks printed on different types of paper are placed in an ozone-resistant accelerated test device that provides an ozone concentration of up to 1 ppm. After a high concentration of 0 ₃ test over time T = 24 hours, the OD of each sample is tested. Value, using formula (6-2) to calculate the color density retention rate OD _b % of the sample after high concentration 0 ₃ test:

OD _b %=OD _T /OD ₀ X 100% (6-2)

OD. The initial OD value of the sample before it was tested

Evaluation criteria: OD _b value between 80 - 100; 〇

001 ₅ values between 70 and 80; 〇

OD _b value between 50 - 70; △

OD _b value is less than 50; X

The test results are shown in Table 1-2. Table 1 UV resistance test

Table 2 ozone resistance test

As can be seen from the comparison of the data in Table 1-2, the dye synthesized by the present invention greatly exceeds the commercially available commercial dye hydrolysis CI active red 180 in terms of anti-UV and anti-O ₃ properties.

In addition, the dye of the present invention is superior to the commercially available commercial hydrolyzed dye C.I. Reactive Red 180 in terms of wet fastness and storage stability.

Claims

The patent requires a phthalimide dye compound of the formula (I):

Wherein: the naphthalene ring structure is directly bonded to the nitrogen atom of the diimide by a tertiary carbon atom;

Ri and R ₂ are each independently H or a water-soluble group attached to the naphthalene ring;

R ₃ , , R ₅ and independently of each other are selected from neutral substituents or water-soluble groups;

n and m are the number of and R ₂ , respectively, and n and m are integers not less than 2.

The dye compound according to claim 1, wherein the naphthalene ring structure is directly bonded to the nitrogen atom of the diimide via a tertiary carbon atom at the 2-position on the naphthalene ring.

3. A dye compound according to claim 1 or 2, characterized in that:

And R ₂ are each independently a water-soluble group attached to the naphthalene ring at any position other than the 2-position.

The dye compound according to claim 1 or 2, wherein the water-soluble group is selected from the group consisting of: SO ₃ H, COOH, SO ₃ M or COOM, wherein M is a cation, and M is selected from the group consisting of: Li ⁺ , Na ⁺ , K ⁺ , imidazolium cation or N ⁺ (R) ₄ , wherein R is H, CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH(CH ₃ ) or CH ₂ CH ₂ CH ₂ CH ₃ .

The dye compound according to claim 4, wherein the water-soluble group is SO ₃ H or SO ₃ M.

The dye compound according to claim 1 or 2, wherein the neutral substituent is selected from the group consisting of: H, a cyano group or a halogen atom.

7. A method of preparing a compound of the formula (I) a phthalimide dye, comprising the steps of:

(II) A substituted ruthenium tetracarboxylic dianhydride compound of the formula (m) is obtained:

(m)

(b) reacting a substituted perylenetetracarboxylic dianhydride of the formula (m) with an aminopolysulfonic acid compound of the formula (IV) under the following reaction conditions:

(IV)

The reaction is carried out in the presence of the catalyst Zn(C3⁄4COO) ₂ · 2Η ₂ 、 under an inert gas in an organic solvent; the substituted fluorene tetracarboxylic dianhydride of the formula (ΠΙ), the amino polysulfonic acid compound of the formula (IV) The molar ratio of the catalyst to the organic solvent is 1:3-10: 0.55~0.94:6~20, and the organic solvent is selected from one or more of imidazole, N-methylpyrrolidone or quinoline, and the reaction temperature is 100- 240 ° C, the reaction time is 1-12 hours;

The product obtained by the reaction is dissolved in water, filtered, and precipitated, and finally filtered to give a solid compound of formula (I).

The method according to claim 7, wherein the water is separated while the reaction is carried out, and the solvent is distilled off together with the water formed in the reaction by distillation.

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, paints, lacquers, laser-printed toners, markers, paper, fabrics, glass, ceramics, or polymers.