WO2000037567A1

WO2000037567A1 - Azo dyes

Info

Publication number: WO2000037567A1
Application number: PCT/EP1999/009554
Authority: WO
Inventors: Klaus Kunde; Michael-Thomas Jörss; Peter Wild
Original assignee: Bayer Aktiengesellschaft
Priority date: 1998-12-18
Filing date: 1999-12-07
Publication date: 2000-06-29
Also published as: DE19858730A1; EP1141139A1; JP2002533519A; AU3035900A

Abstract

The invention relates to compounds which in the free acid form have the formula (I) in which the substituents have the meanings given in the description. Said compounds are extremely well suited for use as ink-jet inks.

Description

Azo dyes

The invention relates to new azo dyes, a process for their preparation and their use for dyeing and printing paper and other materials, in particular as a dye in Ik jet inks.

The dyes according to the invention have the formula in the form of their free acids

(I)

wherein

R represents hydrogen or optionally substituted C _] -C ₆ alkyl,

R ¹ denotes optionally substituted C ¹ -C 6 -alkyl or optionally substituted phenyl,

m represents 0 or 1 and

T ¹ and T ² independently of one another represent OR ⁵ , NR ⁶ R ⁷ or SR ⁸ ,

wherein

R ⁵ and R ⁸ independently of one another are hydrogen, Ci-Cg-alkyl, C ₂ -C ₆ -alkyl substituted by sulfo, carboxy, and / or di-Ct-C -alkylamino or phenyl optionally substituted by C _r C ₄ alkyl, C _r C ₄ alkoxy, sulfo, F, Br and / or Cl,

R ⁶ are hydrogen, C ₆ alkyl or optionally substituted by sulfo, hydroxy, C _r C ₃ - alkoxy, amino or mono- or di-Cι-C3-alkylamino-substituted C ₂ -C ₆ alkyl,

R ⁷ independently of R ^{6 has} the meaning of R ⁶ or optionally substituted by C _r C ₄ alkyl, -CC alkoxy, carboxy, sulfo, F, Cl and / or Br is phenyl or naphthyl or

R ⁶ and R ⁷ together with the N-atom to which they are attached form a morpholine radical or an unsubstituted or substituted by Cj-C ₄ alkyl, C ₂ -C ₄ hydroxyalkyl or _{C2-C4-aminoalkyl-substituted} piperazine .

Examples of substituents for optionally substituted alkyl radicals are, for example: OH, NR ³ R ⁴ , where R ³ and R ^{4 are} independently of one another

Hydrogen, C _r C ₄ alkyl, C ₂ -C ₄ hydroxyalkyl.

Examples of substituents for optionally substituted phenyl are, for example: C _r C ₆ alkyl, C _r C ₆ alkoxy, COOH, SO ₃ H, F, Cl, Br.

Preferred dyes of the formula (I) are those in which

R represents hydrogen, C, -C ₆ alkyl or C ₂ -C ₄ hydroxyalkyl,

R ¹ C _j -C ₆ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₄ aminoalkyl, in particular C ₂ -C ₄ alkyl substituted by NR ³ R ⁴ , wherein R ³ and R ⁴ independently of one another represent hydrogen, C _j -C ₄ alkyl and C ₂ -C ₄ hydroxyalkyl, or optionally by C _r C alkyl, C _r C alkoxy, COOH, SO3H, F, Cl and / or Br is substituted phenyl and

T ¹ and T ^{2 have} the meaning given above.

Compounds of the formula (I) which correspond to the formula (II) are particularly preferred

wherein

R, R ¹ , T ¹ , T ² and m have the meanings given above.

In a preferred embodiment, the substituents of the compound of the formulas (I) and (II) have the following meanings:

R ¹ preferably denotes CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₂ H ₄ OH, C ₂ H ₄ SO ₃ H, C ₃ H ₆ OH, C ₃ H ₆ SO ₃ H, C ₂ H ₄ COOH , C ₃ H ₆ COOH, C ₆ H ₅ , C ₆ H ₄ SO ₃ H, C ₆ H ₄ COOH or C ₂ H ₄ N (CH ₃ ) ₂ ,

R is preferably hydrogen, CH ₃ , C ₂ H ₅ or CH OH,

R ³ and R ⁴ independently of one another are preferably hydrogen, CH ₃ or C ₂ H ₄ OH, R ⁵ is preferably derived from the following compounds HÖR ⁵ : ethylene glycol, isethionic acid (2-hydroxyethanesulfonic acid) or water,

R ⁶ preferably denotes hydrogen, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₂ H ₄ OH, C ₂ H ₄ OCH ₃ or C ₃ H ₆ OH,

R ⁷ preferably denotes hydrogen, C ₂ H ₄ OH, C ₃ H ₆ OH, C ₂ H ₄ SO ₃ H, C ₂ H ₄ COOH, C ₃ H ₆ SO ₃ H, C ₃ H ₆ COOH, C ₆ H ₅ , C ₆ H ₄ SO ₃ H, C ₆ H ₄ COOH or

R ⁶ and R ⁷ together with the N atom to which they are attached preferably form a radical of the formula

- NO - N N-CH, - N NC ₂ H, OH

R ⁸ is preferably derived from the following thiols HSR ⁸ : 2-mercaptoethanol or 3-mercapto-1-propanesulfonic acid,

R ⁹ preferably denotes hydrogen, CH ₃ or CH ₄ OH,

T ¹ and T ² are preferably derived independently of one another from the following amines Tinen and T ² H:

2-aminoethanol, 2-methylaminoethanol, l-amino-2-propanol, 2-amino-l-propanol, diethanolamine, taurine, N-methyl taurine, glycine, 3-aminopropanoic acid, 3-dimethylamino-l-propylamine, N- 2-hydroxyethyl-piperazine, N-2-aminoethylpiperazine, morpholine, aniline, orthanilic acid, methanilic acid, sulfanilic acid, anthranilic acid, 3-aminobenzoic acid, 4-aminobenzoic acid or ammonia. Compounds of the formula (III) are very particularly preferred

wherein

R is hydrogen, CH ₃ or C ₂ H ₅ ,

R ^{1 represents} CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ or C ₆ H ₅ and

T ¹ and T ^{2 have} the meanings given above, preferably for OH, NH ₂ ,

NH ₂ C ₂ H ₄ OH, N (C ₂ H ₄ OH) ₂ , NHC ₂ H ₄ SO ₃ H or CH ₂ NC ₂ H ₄ SO ₃ H.

The dyes of the formula (I) are preferably used in the form of their lithium, sodium, potassium or ammonium salts. Particularly suitable ammonium salts are those in which 1 to 4 hydrogen atoms are replaced by identical or different Ci-Cg-alkyl groups or C ₂ -Cg-alkyl groups substituted by hydroxyl or C ₁ -C 3 -alkoxy groups. Alkanolammonium salts such as methyldiethanolammonium, dimethylethanolammonium or triethanolammonium and quaternary ammonium ions such as tetramethylammonium or tetraethylammonium are particularly preferred.

The invention further relates to a process for the preparation of the compounds of the formula (I) according to the invention, which is characterized in that compounds of the formula (IV)

wherein

R, R ¹ and m have the meanings given above, with compounds of the formula (V)

implements what

X stands for Cl or F or

with 2,4,6-trifluoro- or 2,4,6-trichloro-l, 3,5-triazines and in these reaction products in the 4- and / or 6-position, there are still fluorine or chlorine atoms by reaction with compounds HT ¹ and HT ² in any order, where T ¹ and T ^{2 have} the meaning given above.

The compounds of formula (IV) are described for example in DOS 30 22 972 or can be obtained in an analogous manner. The conditions for the reaction of compounds of formula (IV) with 2,4,6-trifluoro or 2,4,6-trichloro-1,3,5-triazine are also known (for example DE-A 29 35 681 , EP-65 479).

Likewise, the conditions for the conversion of fluorine or chlorine atoms still present in the 4- and 6-position in these triazine-containing reaction products known with NH, OH or SH-containing nucleophiles (EP-755 984, WO 96/24 635, EP-682 088).

The compounds of formula (I) according to the invention can be used as solid or liquid dye preparations. They are preferably used in the form of aqueous preparations, especially solutions. These aqueous dye preparations generally contain one or more dyes of the formula (I), optionally suitable organic solvents, including hydrotropic compounds, and further auxiliaries and / or stabilizers. It is advantageous to prepare the aqueous dye solutions in the course of the dye synthesis itself, without intermediate isolation of the dye.

The application form of the aqueous dye preparations is particularly preferred when dyeing or printing paper. A stable, aqueous, concentrated dyeing preparation can be prepared in a general manner by dissolving the

Dye in water, optionally with the addition of one or more auxiliaries, e.g. a hydrotropic compound or a stabilizer.

The aqueous dye preparations generally contain about 0.5 to 20% by weight of one or more dyes of the formula (I) and 80 to 99.5% by weight

Water and / or solvent and, if appropriate, other customary constituents.

Preferred organic solvents are alcohols and their ethers or esters, carboxamides, ureas, sulfoxides and sulfones, especially those with molecular weights <200 g / mol. Particularly suitable solvents are, for example: methanol, ethanol, propanol; Ethylene, propylene, diethylene, thio-diethylene and dipropylene glycol; Butanediol; ß-hydroxypropionitrile, pentamethylene glycol, ethylene glycol monoethyl and propyl ether, ethylene diglycol monoethyl ether, triethylene glycol monobutyl ether, butyl polyglycol, formamide, triethylene glycol, 1,5-pentanediol, 1,3,6-hexanetriol, 2-hydroxyethyl acetic acid (2'-ethyl acetate, acetic acid 2-ethyl acetate, hydroxy) ethyl ester, glycerin, glycol acetate, 1, 2-dihydroxypropane, l-methoxy-2- propanol, 2-methoxy-l-propanol, N, N-dimethylfornamide, pyrrolidone, N-methylcaprolactam, ε-caprolactam, N-methylcaprolactam, butyrolactone, urea, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, N, N'-dimethylolpropylene urea, dimethyl sulfoxide, dimethyl sulfone, sulfolane, isopropanol and polyethylene glycol.

Other suitable additives for aqueous dye preparations, especially for printing inks, are those ionic or nonionic substances with which the viscosity and / or surface tension can be adjusted to the ranges required for the application, such as anionic, cationic or neutral surfactants such as dispersants and Viscosity regulators. The function of

Viscosity regulators can, for example, be adopted from organic solvents.

Aqueous dye preparations, in particular dye solutions, are preferred

0.5 to 20% by weight, in particular 1 to 15% by weight, of one or more dyes, at least one of the formula (I) or a salt thereof,

50 to 99.5% by weight, in particular 85 to 99% by weight of water,

0 to 30% by weight, in particular 0 to 20% by weight, of one or more organic solvents,

0 to 30% by weight, in particular 0 to 10% by weight, additives influencing the viscosity and / or the surface tension,

the sum of the ingredients mentioned preferably adding up to 100% by weight. The aqueous dye preparations can by dissolving the dye salts in water or from the condensation solutions, which are optionally subjected to isomer exchange and / or desalination, for example by pressure permeation and / or by adding one or more of the above-mentioned organic solvents, if appropriate at elevated temperatures (30 to 100 ° C, in particular 30 to 50 ° C) and with the addition of inorganic and organic bases; if appropriate, conventional ionic or nonionic additives can also be used, for example those with which the viscosity can be reduced and / or the surface tension can be increased.

Instead of the salts of (I), the corresponding free acids can also be used in combination with at least equimolar amounts of the corresponding organic or organic bases.

The aqueous dye preparations according to the invention are also suitable for

Production of printing inks, which can also be used in particular as recording liquids according to the ink jet method.

Another object of the invention is therefore printing inks containing at least one dye (I) and their use as recording liquid for ink

Jet recording systems for producing red prints.

The ink jet method of the method according to the invention is understood to mean an ink jet recording method in which the ink drops are sprayed onto the substrate. The fine ink droplets can be produced by different methods. They are preferably produced using the generally known thermal jet, bubble jet, piezo jet or valve ink jet processes.

When using the dyes according to the invention in the form of their aqueous preparations, in particular their printing inks as recording liquid for inkjet

Recording systems have the following advantages: The physical properties properties such as viscosity, surface tension and the like are in the appropriate ranges; the recording liquid does not cause clogging in fine discharge ports of ink jet recorders; it provides high density images; during storage there is no change in physical and physical properties in the recording liquid

Deposition of solid components; the recording liquid is suitable for recording on various recording media without restrictions on the type of recording media; finally, the recording liquid fixes quickly and results in images with excellent water resistance, light fastness, abrasion resistance and resolution.

The following production examples are intended to illustrate the present invention without, however, restricting it thereto. In the examples, parts are always parts by weight unless otherwise specified.

The dyeings or prints obtained with the dyes according to the invention, in particular the prints which were obtained on paper by the inkjet method, have excellent wet fastness properties.

Examples

example 1

45.2 g of the compound of the formula

are dissolved with the help of soda in 1000 ml of water until neutral. After adding 19 g of 2,4,6-trichloro-1,3,5-triazine, the mixture is stirred at 0-5 ° C., the pH being kept at 7.5 by adding sodium carbonate solution. After the condensation has ended, 13 g of taurine are added; the batch is heated to 40 ° C., the pH being kept at 7.5-8 by adding sodium carbonate solution. After the second condensation has ended, 1 1 g of diethanolamine is added; the batch is heated to boiling until the third condensation has ended.

The resulting solution of the dye of the formula

is largely desalted in a pressure permeation plant and concentrated at the end until the E) value of the absorption maximum is 40 (λ _max = 537 nm).

E ^ value: standardized absorbance of a 1% solution (water) with a layer thickness of 1 cm.

Example 2

10 g of the concentrated solution from Example 1 are stirred with 70 g of water and 20 g of 1,5-pentanediol. An ink is obtained which, when printed with a commercially available ink jet printer, delivers red, brilliant, light-fast records on commercially available paper.

The following table lists other dyes for the preparation of which the specified compounds for the second and third condensation on 2,4,6-trichloro-

1,3,5-triazine can be used.

The resulting solutions contain the dyes of the formulas

Example 3

Example 4

Example 5

game 6

Example 7

Claims

claims

1. Compounds which have the formula (I) in the form of their free acid

wherein

R represents hydrogen or optionally substituted C _j -C ₆ alkyl,

R ^{1 is} optionally substituted C ₁ -C ₆ -alkyl or optionally substituted phenyl,

m represents 0 or 1 and

wherein

R ⁵ and R ⁸ independently of one another are hydrogen, C _j -C ₆ alkyl, C ₂ -C ₆ alkyl substituted by sulfo, carboxy and / or di-C] -C ₃ alkylamino or optionally by C _r C ₄ - Alkyl, C _r C ₄ -alkoxy, sulfo, F, Br and / or Cl are substituted phenyl, R ^{6 is} hydrogen, CpCg-alkyl or optionally substituted by sulfo, hydroxy, C _] -C ₃ -alkoxy, amino or mono- or disubstituted -CC-C3-alkylamino-substituted C ₂ -Cö-alkyl,

R ⁷ independently of R ^{6 has} the meaning of R ⁶ or optionally phenyl or naphthyl which is substituted by C _r C ₄ alkyl, C _r C ₄ alkoxy, carboxy, sulfo, F, Cl and / or Br or

R ⁶ and R ⁷ together with the N atom to which they are attached, a morpholine residue or one optionally substituted by C _j -C alkyl, C -C -

Hydroxyalkyl or C ₂ -C ₄ aminoalkyl substituted piperazine radical.

2. Compounds according to claim 1, characterized in that

R for hydrogen, C. -C ₆ alkyl or C ₂ -C ₄ hydroxyalkyl,

R ^{1 is} C _] -C ₆ alkyl, C ₂ -C ₄ hydroxyalkyl or C ₂ -C ₄ aminoalkyl, in particular C ₂ -C ₄ alkyl substituted by NR ³ R ⁴ , wherein

R ³ and R ⁴ independently of one another are hydrogen, C _r C ₄ alkyl and C ₂ -C ₄ - hydroxyalkyl, or optionally by C ₁ -C ₄ alkyl, CC - alkoxy, COOH, SO ₃ H, F, Cl and / or Br is substituted phenyl and

T ¹ and T ^{2 have} the meaning given above.

3. Compounds according to claim 1, characterized in that they correspond to the formula (II)

wherein

R, R ¹ , T ¹ , T ² and m have the meanings given in claim 1.

4. Compounds according to claim 1, characterized in that

R ¹ CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₂ H ₄ OH, C ₂ H ₄ SO ₃ H, C ₃ H ₆ OH, C ₃ H ₆ SO ₃ H, C ₂ H ₄ COOH, C ₃ H ₆ COOH, C ₆ H ₅ , C ₆ H ₄ SO ₃ H, C ₆ H ₄ COOH or C ₂ H ₄ N (CH ₃ ) ₂ ,

R represents CH ₃ , C ₂ H ₅ or C ₂ H ₄ OH,

R ³ and R ⁴ independently of one another denote hydrogen, CH ₃ or C ₂ H ₄ OH,

R ^{5 is} derived from the following compounds HÖR ⁵ : ethylene glycol, isethionic acid (2-hydroxyethanesulfonic acid) or water,

R6 denotes hydrogen, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₂ H ₄ OH, C ₂ H ₄ OCH ₃ or C ₃ H ₆ OH,

R ⁷ hydrogen, C ₂ H ₄ OH, C ₃ H ₆ OH, C ₂ H ₄ SO ₃ H, C ₂ H ₄ COOH, C ₃ H ₆ SO ₃ H, C ₃ H ₆ COOH, C ₆ H ₅ , C ₆ H ₄ SO ₃ H or C ₆ H ₄ COOH means or R ⁶ and R ⁷ together with the N atom to which they are attached form a radical of the formula

- NO. - N-CH, - N NC ₂ H ₄ OH

W

or - form _N \ / NC, 2H, 4NH, 2,

R ^{8 is} derived from the following thiols HSR ⁸ : 2-mercaptoethanol or 3-mercapto-1-propanesulfonic acid,

R9 is hydrogen, CH ₃ or C ₂ H ₄ OH and,

T ¹ and T ² are derived independently of one another from the following amines TH and T ² H:

2-aminoethanol, 2-methylaminoethanol, 1-amino-2-propanol, 2-

Amino-1-propanol, diethanolamine, taurine, N-methyl taurine, glycine, 3-aminopropanoic acid, 3-dimethylamino-l-propylamine, N-2-hydroxyethyl-piperazine, N-2-aminoethylpiperazine, morpholine, aniline, orthanilic acid, Methanilic acid, sulfanilic acid, anthranilic acid, 3-aminobenzoic acid, 4-aminobenzoic acid or ammonia.

5. Compounds according to claim 1, characterized in that they are the

Correspond to formula (III)

wherein

R is hydrogen, CH ₃ or C ₂ H ₅ ,

Rl represents CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ or C ₆ H ₅ and

T ¹ and T ^{2 have} the meanings given in claim 1, preferably for OH, NH ₂ , NH ₂ C ₂ H ₄ OH, N (C ₂ H ₄ OH) ₂ , NHC ₂ H ₄ SO ₃ H or

CH ₂ NC ₂ H ₄ SO ₃ H stand.

6. Compounds according to claim 1, characterized in that they are in the form of their lithium, sodium, potassium or ammonium salts.

7. A process for the preparation of compounds according to claim 1, which is characterized in that compounds of the formula (IV)

wherein R, R ¹ and m have the meaning given in claim 1, with compounds of the formula (V)

implements what

X stands for Cl or F or

with 2,4,6-trifluoro- or 2,4,6-trichloro-l, 3,5-triazines and in these reaction products in the 4- and / or 6-position there are still fluorine or chlorine atoms by reaction with compounds HT ¹ and HT ² in any order, where T ¹ and T ^{2 have} the meaning given above.

Containing aqueous dye preparations, in particular dye solutions

0.5 to 20% by weight of one or more dyes, at least one of which corresponds to the compound of claim 1 or a salt thereof,

50 to 99.5% by weight of water, 0 to 30% by weight of one or more organic solvents,

0 to 30% by weight of additives which influence the viscosity and / or the surface tension.

9. printing inks containing at least one dye which corresponds to a compound according to claim 1.

10. Use of the compounds of claim 1 for dyeing and printing to substrates containing hydroxyl and / or amide groups, in particular for printing paper by the ink-jet method.