EP1615973A1

EP1615973A1 - Methanesulfoamide azo dye

Info

Publication number: EP1615973A1
Application number: EP04724549A
Authority: EP
Inventors: Dominique Pflieger; Hans Joachim Metz
Original assignee: Clariant GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 2003-04-10
Filing date: 2004-03-31
Publication date: 2006-01-18
Also published as: WO2004090045A1; US7220843B2; CA2521861A1; US20060286477A1; JP2006524274A; DE10316402A1; CN1771297A; BRPI0409226A; KR20060013501A

Abstract

The invention relates to monoazo, disazo and trisazo colorants of formula (I), wherein M represents two hydrogen atoms or a metal ion selected from the group consisting of Cu, Co, Ni, Mn, Zn and Al, and A represents the radical of a substituted naphthyl radical or pyrazolyl radical.

Description

description

Methanesulfonamide azo dyes

The present invention describes new azo dyes containing methanesulfonamide groups, processes for their preparation and their use in recording liquids, in particular for the inkjet process (ink-jet printing).

The inkjet process is a non-contact printing process, generally distinguishing between two printing techniques: drop-on-demand and continuous stream. The drop-on-demand principle is based on the fact that the ink in the form of a drop from a nozzle - electronically controlled - is placed in the right place at the right time, whereas with continuous stream printing the ink is permanently released and then, also after electronic charging either hits the recording medium (e.g. paper), or is distracted into a receptacle. In order to obtain prints with high sharpness and good resolution, the recording liquids or the dyes contained therein must meet corresponding requirements, in particular with regard to lightfastness and waterfastness. High lightfastness is particularly important for ink-jet applications outdoors and in the production of ink-jet prints with photographic quality.

The most important role is played by the dyes used in the inks. Although a large number of dyes have been developed, there are only a few that meet the requirements of a modern printing process.

A group of chrome complex dyes is characterized by high light fastness, but is ecologically questionable due to the chromium content.

There is therefore a need for improved colorants which are ecologically harmless and are highly soluble in water and / or organic solvents, good ozone and light fastness, high color strength and brilliance.

It has been found that certain azo dyes containing methanesulfonamide groups solve this problem.

The present invention therefore relates to compounds of the general formula (I)

wherein

M represents two hydrogen atoms, or a metal ion from the group Cu, Co, Ni,

Mn, Zn and AI means;

A the meaning

R ^{1 is} H, OH or -NH- (CH ₂ ) a-SO ₃ ^" X ⁺ with a equal to 1 to 6, preferably

2, 3 or 4;

R ^{2 has} the meaning H or a radical of the formulas

[S0 ₃ -] _n v

is

D is C ₆ H, C ₆ H ₃ (OH) or C ₆ H ₃ (OCH ₃ );

X is H, alkali metal, preferably Na or K; NH ₄ , -C ₁₈ alkyl NH ₃ ,

(-C ₈ -C alkyl) ₂ NH2 _> (-C ₁₈ alkyl) 3NH, (-C ₁₈ alkyl) ₃ CNH ₃ , (CrC ₈ alkyl) ₂ CHNH3, or (C ₈ -C alkyl) _{4 has} N and n is a number from 1 to 4, preferably 1 or 2.

Compounds of the formula (I) in which M denotes two hydrogen atoms (metal-free compound) or the meaning Cu are preferred.

Monoazo compounds of the formulas (IIIa) to (IIf) are particularly preferred,

SO ₃ X

wherein X, a and n have the meanings given above.

Disazo compounds of the formulas (purple) and (Mlb) are also particularly preferred,

(purple)

(IIIb)

wherein X and n have the meanings given above.

Trisazo compounds of the formulas (IVa) and (IVb) are also particularly preferred,

(IVb)

wherein R ¹ and X have the meanings given above.

The present invention also relates to a process for the preparation of the compound of the formula (I), characterized in that 2-di (methanesulfonyl) amidoaniline is diazotized, the resulting diazonium salt is coupled with a coupling component corresponding to the ring system A, and one of the two methanesulfonamide groups is split off and optionally reacting the azo compound formed with a Cu, Co, Ni, Mn, Zn or Al salt.

The starting compound 2-di (methanesulfonyl) amidoaniline can be prepared by reacting 2-nitro-aniline with at least two equivalents of methanesulfonyl chloride in an excess of pyridine and then reducing the nitro group, for example with iron or tin in hydrochloric acid / ethanol. The diazotization and coupling steps can be carried out by customary methods.

The diazotization is preferably carried out in aqueous solution or suspension

Sodium nitrite at temperatures from 0 to 10X and a pH between 1 and

3 performed.

The azo coupling is preferably added in aqueous solution or suspension

Temperatures from 0 to 20X and a pH between 3 and 9 are carried out.

The molar ratios between the respective diazonium salt and the respective coupling component are preferably 1: (0.8 to 2).

One of the two methanesulfonamide groups is split off selectively by heating in an aqueous alkaline medium, pH preferably 9 to 12, to about 60 to 80X.

The complexation is conveniently done by adding an aqueous metal salt solution, e.g. Metal sulfate, chloride, bromide, hydrogen sulfate, bicarbonate or carbonate, where metal has the meaning given above, particularly preferably copper. Depending on the respective dye, the complexation can be carried out in the acidic as well as in the basic range. The temperature should be between 60 and 130X, if necessary heated under pressure.

To prepare disazo dyes according to the invention, the corresponding monoazo dye containing the methanesulfonyl group can first be prepared as described above and the free amino group on the naphthyl radical of A can then be diazotized and coupled. The resulting disazo dye can then be complexed with a metal salt as described above.

To produce trisazo dyes according to the invention, the corresponding disazo dye can first be prepared as described above and then the free amino group on the phenyl radical D can be diazotized and coupled.

However, it is also possible to contain the methanesulfonyl group

Diazotize monoazo dye and with an appropriate phenylazo to couple naphthalenesulfonic acid salt, or to couple the monoazo dye containing the methanesulfonyl group with a diazotized phenylazo-naphthalenesulfonic acid salt.

The resulting trisazo dye can then be complexed with a metal salt as described above.

However, it is also possible to use the already complexed monoazo dye instead of the monoazo dye in the above-mentioned synthesis variants.

To exchange the cations on the sulfo groups, the azo dye can be replaced with a

Solution of the corresponding salt, e.g. a substituted ammonium salt.

The dyes of the invention can be isolated from the initially obtained, preferably aqueous, reaction mixtures by salting out, filtering or spray drying, if appropriate after partial or complete desalination by means of membrane filtration. However, isolation can also be dispensed with and the reaction mixtures containing the dyes according to the invention can be converted directly into concentrated dye solutions by adding organic and / or inorganic bases and / or humectants and, if appropriate, after partial or complete desalination by means of membrane filtration. Alternatively, the complex dyes can also be used as a press cake (optionally also in a flush process) or as a powder. For further purification, the dyes can be passed over an ion exchange resin in the form of their aqueous solutions.

To set certain color shades, the dyes according to the invention can be shaded with a further colorant, preferably from the group of colorants listed in the Color Index, such as, for example, Cl Acid Yellow 17 and 23, Cl Direct Yellow 86, 98 and 132, Cl Reactive Yellow 37, Cl Pigment Yellow 17, 74, 83, 97, 120, 139, 151, 155 and 180; Cl Direct Red 1, 11, 37, 62, 75, 81, 87, 89, 95, 227; CJ. Acid Red 1, 8, 80, 81, 82, 87, 94, 115, 131, 144, 152, 154, 186, 245, 249 and 289; Cl Reactive Red 21, 22, 23, 35, 63, 106, 107, 112, 113, 114, 126, 127, 128, 129, 130, 131, 137, 160, 161, 174, 180; Cl Pigment Red 122, 176, 184, 185 and 269; Cl Direct Blue 199, Cl Acid Blue 9, Cl Pigment Blue 15: 1-15: 4. The shading colorant is preferably added in an amount of 0.001 to 5% by weight, in particular 0.01 to 1% by weight, based on the dry weight of the dye according to the invention.

The dyestuffs according to the invention can be mixed with the shading colorant by mixing the dyestuffs of the formula (I) and the shading colorant in the stated mixing ratios in the form of dry powders, their solutions, water- or solvent-moist presscakes and / or masterbatches, or from the dyes manufactured inks nuanced.

The present invention also relates to the use of the (optionally nuanced) dyes of the formula (I) for dyeing and printing natural and synthetic fiber materials, such as e.g. Polyester, silk, wool or blended fabrics, in particular for recording writing and images on various recording media, as well as for dyeing paper or cellulose in bulk.

The dyes described are prepared in accordance with the requirements mentioned for use in recording liquids. The dyes can be isolated from the initially obtained, preferably aqueous, reaction mixtures by salting out and filtering or by spray drying, if appropriate after partial or complete desalination by means of membrane filtration and / or ion exchange. However, isolation can also be dispensed with and the reaction mixtures containing dyes can be converted directly into concentrated dye solutions by adding organic and / or inorganic bases, possibly humectants, preservatives and, if appropriate, after partial or complete desalination by means of membrane filtration. Alternatively, the dyes can also be used as a press cake (optionally also in a flush process) or as a powder. The dyes according to the invention are advantageously as pure as possible and salt-free form, ie free of NaCl or other customary inorganic salts which have arisen in the synthesis of the dyes.

Inorganic bases suitable for concentrated dye solutions are, for example, lithium hydroxide, lithium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium hydroxide, potassium carbonate and ammonia. Suitable organic bases are, for example, monoethanolamine, diethanolamine, triethanolamine, 2-aminopropanol, 3-aminopropanol, dipropanolamine, tripropanolamine, N-methylaminoethanol, N, N-dimethylamino ethanol, N-Phenylaminopropanol, ethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, Tetramethylhexylendiamin, diethylenetriamine, triethylenetetramine , Triethylamine, diisopropylethylamine and polyethyleneimine.

Moisturizers suitable for concentrated dye solutions are, for example, formamide, urea, tetramethylurea, ε-caprolactam, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, butyl glycol, methyl cellosolve, glycerol, N-methylpyrrolidone, 1, 3-diethyl-2-nolononolide, sodium-2-imidazolide Cumene sulfonate and sodium butyl monoglycol sulfate.

The dyes according to the invention are particularly suitable for the production of recording liquids, in particular of aqueous and non-aqueous inks for the ink-jet printing process, and for those inks which work according to the hot-melt process or are based on microemulsions, but also for other printing -, duplication, marking, writing, drawing, stamping or registration procedures.

The present invention also relates to recording liquids which contain a dye according to the invention and optionally other colorants for shading, as described above. Such shading colorants are advantageously contained in an amount of 0 to 20% by weight, preferably 0.01 to 10% by weight, in particular 0.1 to 5% by weight, based on the total weight of the recording liquid. The composition of the recording liquid must be adapted to the respective purpose. Recording liquids according to the invention generally contain a total of 0.1 to 50% by weight of the dye of the formula (I), including any shading dye, calculated as dry weight, 0 to 99% by weight of water and 0.5 to 99.5% by weight. % organic solvent and / or humectant. In a preferred embodiment, the recording liquids contain 0.5 to 15% by weight of the said dye, calculated as dry weight, 35 to 75% by weight of water and 10 to 50% by weight of organic solvent and / or humectant; in another preferred embodiment 0.5 to 15% by weight of said dye, calculated as dry weight, 0 to 20% by weight of water and 70 to 99.5% by weight of organic solvent and / or humectant.

Water is preferably used in the form of distilled or deionized water to prepare the dyes (I) and recording liquids containing them.

The solvents and / or humectants contained in the recording liquids can be an organic solvent or a mixture of such solvents, with water-miscible solvents being preferred. Suitable solvents are, for example, monohydric or polyhydric alcohols, their ethers and esters, e.g. Methanol, ethanol, propanol, isopropanol, butanol, isobutanol; di- or trihydric alcohols, in particular with 2 to 6 carbon atoms, e.g. Ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 2,6-hexanetriol, glycerin, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol; lower alkyl ethers of polyhydric alcohols, e.g. Ethylene glycol monomethyl, ethyl or butyl ether, triethylene glycol monomethyl or ethyl ether; Ketones and ketone alcohols such as Acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol; Amides such as Dimethylformamide, dimethylacetamide, N-methylpyrrolidone; also urea, tetramethylurea, thiodiglycol, ε-caprolactam.

Furthermore, the recording liquids according to the invention can also contain conventional additives, for example preservatives, cationic, anionic or non-ionic surface-active substances (surfactants and wetting agents), as well as agents for regulating the viscosity, for example polyvinyl alcohol, cellulose derivatives, or water-soluble natural or artificial resins as film formers or binders to increase the adhesive and abrasion resistance. It can also contain light stabilizers, optical brighteners, oxidizing agents, reducing agents and radical scavengers.

Amines, e.g. Ethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, diisopropylamine, N-ethyldiisopropylamine to increase the pH of the recording liquid may be present, normally based on 0 to 10% by weight, preferably 0.5 to 5% by weight on the total weight of the recording liquid.

The recording liquids for the ink-jet printing process can, depending on the embodiment of this printing process, e.g. as a continuous jet, intermittent jet, pulse jet or compound jet process, further additives, e.g. for buffering the pH value, for adjusting the electrical conductivity, the specific heat, the thermal expansion coefficient and the conductivity.

With regard to viscosity and surface tension, the recording liquids according to the invention are in the ranges suitable for ink-jet processes. They deliver printed images of high optical density with excellent light and water fastness.

Furthermore, the dyes according to the invention can be used as an ink set in combination with black, yellow, magenta, cyan, optionally green and optionally orange colorants.

Preferred is a set of printing inks whose black preparation contains carbon black as a colorant, in particular a gas or furnace carbon black, such as, for example, Cl Reactive Black 8, Cl Reactive Black 31, Cl Direct Black 168, Cl Sol. Sulfur Black 1 and 2, Cl Acid Black 194; whose cyan preparation contains the dyes Cl Acid Blue 9, Cl Direct Blue 199, or a pigment from the group of Contains phthalocyanine, indanthrone or triarylcarbonium pigments, in particular the Color Index pigments Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 16, Pigment Blue 56, Pigment Blue 60 or Pigment Blue 61; whose magenta preparation contains the dyes Cl Reactive Red 23, Cl Reactive Red 180, Cl Acid Red 52, or a pigment from the group of monoazo, disazo, ß-naphthol, naphthol AS-, lacquered azo, metal complex, benzimidazolone -, anthanthrone, anthraquinone, quinacridone, dioxazine, perylene, thioindigo, triarylcarbonium or diketopyrrolopyrrole pigments, in particular the Color Index pigments Pigment Red 2, Pigment Red 3, Pigment Red 4, Pigment Red 5, Pigment Red 9 , Pigment Red 12, Pigment Red 14, Pigment Red 38, Pigment Red 48: 2, Pigment Red 48: 3, Pigment Red 48: 4, Pigment Red 53: 1, Pigment Red 57: 1, Pigment Red 112, Pigment Red 122 , Pigment Red 144, Pigment Red 146, Pigment Red 147, Pigment Red 149, Pigment Red 168, Pigment Red 169, Pigment Red 170, Pigment Red 175, Pigment Red 176, Pigment Red 177, Pigment Red 179, Pigment Red 181, Pigment Red 184, Pigment Red 185, Pigment Red 187, Pigment Red 188, Pigment Red 207, Pigment Red 208, Pigment Red 209, Pigment Red 210, Pi gment Red 214, Pigment Red 242, Pigment Red 247, Pigment Red 253, Pigment Red 254, Pigment Red 256, Pigment Red 257, Pigment Red 262, Pigment Red 263, Pigment Red 266, Pigment Red 269, Pigment Red 274, Pigment Violet 19, Pigment Violet 23 or Pigment Violet 32; whose yellow preparation preferably contains the dye Cl Acid Yellow 17, Cl Acid Yellow 23, Cl Direct Yellow 86, Cl Direct Yellow 98, Cl Direct Yellow 132, Cl Reactive Yellow 37, or a pigment from the group of the monoazo, disazo, Contains benzimidazoline, isoindolinone, isoindoline or perinone pigments, in particular the Color Index pigments Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 16, Pigment Yellow 17, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 81, Pigment Yellow 83, Pigment Yellow 87, Pigment Yellow 97, Pigment Yellow 111, Pigment Yellow 120, Pigment Yellow 126, Pigment Yellow 127, Pigment Yellow 128, Pigment Yellow 139, Pigment Yellow 151, Pigment Yellow 154 , Pigment Yellow 155, Pigment Yellow 173, Pigment Yellow 174, Pigment Yellow 175, Pigment Yellow 176, Pigment Yellow 180, Pigment Yellow 181, Pigment Yellow 191, Pigment Yellow 194, Pigment Yellow 196 or Pigment Yellow 213; whose orange preparation preferably contains a pigment from the group of disazo, β-naphthol, naphthol AS, benzimidazolone or perinone pigments, in particular the Color Index pigments Pigment Orange 5, Pigment Orange 13, Pigment Orange 34, Pigment Orange 36, Pigment Orange 38, Pigment Orange 43, Pigment Orange 62, Pigment Orange 68, Pigment Orange 70, Pigment Orange 72 or Pigment Orange 74; whose green preparation preferably contains a pigment from the group of phthalocyanine pigments, in particular the Color Index pigments Pigment Green 7 or Pigment Green 36.

Furthermore, the dye mixtures according to the invention are suitable as colorants in electrophotographic toners and developers, such as e.g. One-component and two-component powder toners, magnetic toners, liquid toners, polymerization toners and other special toners are suitable.

Typical toner binders are polymerization, polyaddition and polycondensation resins, such as styrene-styrene-acrylate, styrene-butadiene, acrylate, polyester, phenol-epoxy resins, polysulfones, polyurethanes, individually or in combination, and polyethylene and polypropylene, which also contain other ingredients, such as Charge control agents, waxes or flow agents, can contain or can be added afterwards.

Furthermore, the dye mixtures according to the invention are suitable as colorants in powders and powder coatings, in particular in triboelectrically or electrostatically sprayed powder coatings which are used for the surface coating of objects made of, for example, metal, wood, plastic, glass, ceramic, concrete, textile material, paper or rubber.

Epoxy resins typically used are carboxyl- and hydroxyl-containing polyester resins, polyurethane and acrylic resins together with conventional hardeners as powder coating resins. Combinations of resins are also used. For example, epoxy resins are often used in combination with carboxyl- and hydroxyl-containing polyester resins. In addition, the dyes according to the invention are suitable as colorants for color filters, both for additive and for subtractive color production, and as colorants in electronic inks for so-called "electronic newspapers" and in the medical field.

In addition, the azo dyes according to the invention are also suitable as colorants in printing inks, lacquers, paints, artists' colors, plastics, rubber materials, office supplies, wood paints and cleaning agents. Typical printing inks are e.g. Offset printing inks, gravure inks and printing inks for water-based and solvent-based packaging printing and flexographic printing. Typical paints are car series and repair paints, industrial paints and architectural paints (e.g. plastic plasters or dispersion paints). Typical plastic colors are e.g. those in hard and soft PVC (polyvinyl chloride), polyolefins or polystyrenes.

Furthermore, the dyes according to the invention can be used for the surface coating of objects made of, for example, metal, wood, plastic, glass, ceramic, concrete, textile material, paper and rubber.

In the fields of application described above, too, the dyes according to the invention can additionally be shaded with the dyes and / or pigments listed above.

In the examples below, "parts" mean parts by weight. In the formulas below, acidic hydrogen atoms, depending on the pH, can be completely or partially replaced by Na ⁺ or K ⁺ , and vice versa.

Example 1 :

a) Diazotization and coupling:

5.3 parts of 2-di (methanesulfonyl) amidoaniline were added to a mixture of 25 parts

Water and 5.9 parts of 30 wt .-% hydrochloric acid stirred. After adding The amine was diazotized in 10 parts of ice by adding 5 volumes of a 4N sodium nitrite solution. The mixture was allowed to stir at 5 ° C. for 2 hours and the excess nitrite was then destroyed using sulfamic acid. The resulting suspension was then added dropwise to a solution of 8.4 parts of 1,8-dihydroxynaphthalene-3,6-disulfonic acid (disodium salt) in 30 parts of water. The resulting mixture was stirred at room temperature for 2 hours, the voluminous red precipitate of the monoazo dye was filtered off and dried.

b) Demesylation and complexation with Cu:

19.5 parts of the monoazo dye from a) were in 75 parts of water and

9.6 parts of 30 wt .-% sodium hydroxide solution. The solution was left on for 1 hour

Warmed 60X and then added 5.4 parts of sodium acetate. After heating up

During 80X, 5 parts of copper (II) sulfate hydrate were added in small portions

Added for 1 hour, during which a dark red solution of the monoazo

Copper complex dye of the formula

originated. After cooling to room temperature, the dye solution was filtered through a 0.1-0.3 μm filter and then desalted using a membrane desalination plant. Example 2

90 parts of a monoazo copper complex dye solution from Example 1 were mixed with 35 parts of a solution of 7.4 parts of a C ₂ -Cι ₄ alkylamine in 20 parts of water and 4.8 parts of 30 wt .-% hydrochloric acid added. The resulting precipitate was stirred for 1 hour, filtered, the residue washed free of salt with deionized water and dried. 15 parts of a compound of the formula were obtained

alkyl

where "alkyl" means C ₂ -C ₁ alkyl.

Example 3

a) Diazotization and coupling to the monoazo dye:

11.5 parts of 2-di (methanesulfonyl) amidoaniline were added to a mixture of 50 parts

Water and 12 parts of 30 wt .-% hydrochloric acid stirred. After adding

30 parts of ice became the amine by adding 10 parts by volume of a 4N

Sodium nitrite solution diazotized. The mixture was allowed to stir at 5 ° C. for 2 hours and the excess nitrite was then destroyed using sulfamic acid.

The resulting suspension was then in a solution of 10.4 parts

2-amino-8-hydroxynaphthalene-6-sulfonic acid in 100 parts water and 10.8 parts

30% by weight sodium hydroxide solution was added dropwise. By adding 8 parts at the same time

Sodium carbonate was adjusted to a pH of 8.5 to 9.0. The resulting

The mixture was stirred at room temperature for 3 hours, filtered off and dried. b) Diazotization and coupling to the disazo dye:

18.8 parts of the monoazo dye from a) were mixed in a mixture of 200 parts

Water and 29 parts of 30 wt .-% hydrochloric acid stirred. After adding

50 parts of ice became the amine by adding 8 parts by volume of a 4N

The resulting suspension was then in a solution of 8.5 parts

2-hydroxynaphthalene-6-sulfonic acid in 55 parts water and 3.7 parts

30% by weight sodium hydroxide solution was added dropwise. By adding 32 parts at the same time

A pH of 8.5 to 9.0 was set in 30% by weight sodium hydroxide solution. The resulting dark violet mixture was stirred for 3 hours at room temperature. The resulting disazo dye was filtered off and dried.

c) Demesylation and Complexation with Cu:

16.8 parts of the disazo dye from b) were stirred into 50 parts of water and 1.5 parts of 30% strength by weight sodium hydroxide solution. The mixture was warmed to 60X for 1 hour and then 1.5 parts of sodium acetate were added. After heating to 98 ° C., 1.8 parts of copper (II) sulfate hydrate in 10 parts of water were added. The reaction mixture was heated at reflux for 6 hours, giving a violet solution of the disazo copper complex dye of the formula

originated. After cooling to room temperature, the dye solution was filtered through a 0.1-0.3 μm filter and then desalted using a membrane desalination plant. Example 4

67 parts of a disazo copper complex dye solution from Example 3 were mixed with 13 parts of a solution of 2.7 parts of a C ₂ -C ₄ alkylamine in 7 parts of water and 1.8 parts of 30% by weight hydrochloric acid. The resulting precipitate was stirred for 1 hour, filtered, the residue washed free of salt with deionized water and dried. 7.2 parts of a compound of the formula were obtained

where "alkyl" each means -C ₂ -Cu-alkyl.

Example 5

9.7 parts of 2 - [(4-amino-3-methoxyphenyl) azo] -naphthalene-6,8-disulfonic acid disodium salt (CAS No. 65151-26-0) were added to a mixture of 120 parts of water and 5.7 parts 30 wt .-% hydrochloric acid stirred. After adding 50 parts of ice, the amine was diazotized by adding 5.2 parts by volume of a 4N sodium nitrite solution. The mixture was allowed to stir at 5X for 1 hour and then the excess nitrite was destroyed with sulfamic acid. The orange solution was slowly added to a solution of 12.5 parts of the monoazo copper complex dye from Example 1b). A pH of 4.3 to 4.5 was set by simultaneously adding 5 parts of sodium acetate. The resulting mixture was stirred for 3 hours at room temperature using a black solution of the trisazo copper complex dye of the formula

originated. After cooling to room temperature, the dye solution was filtered through a 0.1-0.3 μm filter and then desalted using a membrane desalination plant.

Example 6

200 parts of a trisazo copper complex dye solution from Example 5 were mixed with 60 parts of a solution of 10.3 parts of 2-ethylhexylamine in 40 parts of water and 9.4 parts of 30% by weight hydrochloric acid. The resulting black precipitate was stirred for 1 hour, filtered, the residue washed free of salt with deionized water and dried. 25 parts of a compound of the formula were obtained

Example 7:

In analogy to Example 1, but without the addition of copper salt, the

Compound of the following formula prepared

Example 8:

In analogy to Example 3, but without the addition of copper salt, the

Compound of the following formula prepared

Example 9:

In analogy to Example 5, but without the addition of copper salt, the

Compound of the following formula prepared

Example 10: Preparation of a recording liquid 2.5 g of pure dye according to Example 1 were introduced with stirring at 25 ° C. into a mixture of 20.0 g of diethylene glycol, 1.0 g of triethanolamine, 1.0 g of urea and 78.0 g of demineralized water and solved.

The inks produced in this way deliver magenta-colored printed images with very good light fastness.

Inkjet inks were produced in an analogous manner with the pure dyes from Examples 2 to 9.

The prepared recording liquids are stored at 60X for 4 weeks to investigate the storage stability. No precipitations can be observed after this time, the recording liquids can be finely filtered without residue. Colorimetric studies show no changes to the tests made before the storage stability tests.

Claims

claims:

1) Compounds of the general formula (I)

wherein

M represents two hydrogen atoms, or a metal ion from the group Cu, Co, Ni,

Mn, Zn and AI means;

A the meaning

R ^{1 has} the meaning H, OH or -NH- (CH ₂ ) _a -SO ₃ ^" X ⁺ where a is 1 to 6; R ^{2 has} the meaning H or a radical of the formulas

[SO ₃ "] _n χ _n ⁺

is

D is C ₆ H ₄ , C ₆ H ₃ (OH) or C ₆ H ₃ (OCH ₃ );

X is H, alkali metal, NH ₄ , -C ₁₈ alkyl NH ₃ ,

(C ₁ -Cι ₈ alkyl) ₂ NH _2, (Cι-Cι ₈ alkyl) ₃ NH, (CrCi8-alkyl) ₃ CNH3, (C ₁ -Ci8 alkyl) ₂ CHNH3 _I or (Cι-C ₈ - Alkyl) ₄ N, and n is a number from 1 to 4.

2) Connection according to claim 1, characterized by the formulas (lla) to (llf)

SO ₃ X

3) Connection according to claim 1, characterized by the formulas (purple) or (Mb)

(purple)

(IIIb)

4) Compound according to claim 1, characterized by the formula (IVa) or (IVb)

(IVb) 5) Process for the preparation of a compound according to one or more of claims 1 to 4, characterized in that 2-di (methanesulfonyl) - amidoaniline is diazotized, the resulting diazonium salt is coupled with a coupling component corresponding to the ring system A, one of the two methanesulfonamide groups is split off and optionally reacting the azo compound formed with a Cu, Co, Ni, Mn, Zn or Al salt.

6) Use of a compound according to one or more of claims 1 to 4 for dyeing and printing natural or synthetic fiber materials, for recording writing and images on recording media, for dyeing paper or cellulose in the mass and as a colorant in printing inks, varnishes, Paints, plastics, rubber materials, office supplies, wood painting and cleaning agents and artists' paints.

7) Use according to claim 6 as a colorant in ink-jet inks and electrophotographic toners.

8) recording liquid containing a total of 0.1 to 50 wt .-% of at least one compound according to one or more of claims 1 to 4 and optionally a shading colorant, calculated as dry weight, 0 to 99 wt .-% water and 0.5 to 99 , 5 wt .-% organic solvent and / or humectant.

9) Use of a recording liquid according to claim 8 in an ink set consisting of the colors black, yellow, cyan, magenta, optionally orange and optionally green.