EP2904142A1 - Colorants réactifs et leurs complexes métalliques, leur procédé de production et leur utilisation - Google Patents

Colorants réactifs et leurs complexes métalliques, leur procédé de production et leur utilisation

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Publication number
EP2904142A1
EP2904142A1 EP13731709.5A EP13731709A EP2904142A1 EP 2904142 A1 EP2904142 A1 EP 2904142A1 EP 13731709 A EP13731709 A EP 13731709A EP 2904142 A1 EP2904142 A1 EP 2904142A1
Authority
EP
European Patent Office
Prior art keywords
amino
carbamoyl
sulfamoyl
alkyl
monocycloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13731709.5A
Other languages
German (de)
English (en)
Inventor
Vajiravelu Sivamurugan
Roxana Barbieru
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dystar Colours Distribution GmbH
Original Assignee
Dystar Colours Distribution GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dystar Colours Distribution GmbH filed Critical Dystar Colours Distribution GmbH
Priority to EP13731709.5A priority Critical patent/EP2904142A1/fr
Publication of EP2904142A1 publication Critical patent/EP2904142A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/022—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring the heterocyclic ring being alternatively specified
    • C09B62/026—Azo dyes
    • C09B62/032—Metal complex azo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/443—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being alternatively specified
    • C09B62/447—Azo dyes
    • C09B62/455—Metal complex azo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group

Definitions

  • Reactive dyes and their metal complexes process for fhe production thereof and their use
  • the present invention relates to the technical fieldof reactive dyestuffs and their metal complexes for dyeing and printing of hydroxyl-, amino-, and carboxamido-containing material.
  • Metal complex reactive dyes based on bis and polyazo moiety containing at least one anchor are known from prior art and can be used as colorants in different applications, see for example DE3514969, DE3515407, US5319074, US3450689, US3462409, US3457251 , US3457252, GB1279283, GB1553474, WO2003104335, US5527886, DE3519551 and US4939243.
  • the known dyes have a number of technical disadvantages such as low fixation, moderate wet fastness and light fastness level. Hence, there is a need for developing new reactive dyes of superior technical performance.
  • the dyes of the formula (I) as described below show highly advantageous properties over the known dyes. These include superior wet fastness and light fastness, superior ecological profile as well as the possibility to achieve a wide range of shades including dark violets, dark browns, navy and blacks.
  • the present invention refers to dyes of the formula (I) and mixtures thereof
  • n is an integer 0 or 1 ;
  • K is a radical of coupling heterocyclic component as described below;
  • A is a radical of middle component as described below when n is 1 and has the meaning of B when n is 0;
  • B is a radical of diazo component as described below;
  • M is hydrogen, lithium, sodium, potassium, ammonium or mono-, di-, tri- or tetra-(Ci- C 4 )-alkylammonium, one equivalent of an alkali earth metal, or a monovalent organic cation;
  • K is a coupling component of following general formulae (K1 ) to (K3);
  • R 1 and R 4 independent from each other, are hydrogen, alkyl, cycloalkyl,
  • R 3 ', R 6 to R 9 and R 12 independent from each other are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, ⁇ , ⁇ -dicycloalkyl-carbamoyl, N,N- dialkyl-carbamoyl, N-monoaryl-carbamoyl, ⁇ , ⁇ -diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicyclo
  • X is vinyl or a radical -CH 2 CH 2 -Y where Y is a group removable under alkaline conditions,which will leave the molecule under alkaline conditions to yield the vinyl sulfone function.
  • groups are OS0 3 M, SS0 3 M, OCOCH 3 , OP0 3 M and halogen;
  • R 10 is hydroxyl or amino group
  • the point of attachment and R 5 can be positioned ortho or para to the amino rest bearing the substituents R 6 and R 7 , meaning that when the point of attachment is positioned ortho to amino rest bearing the substituents R 6 and R 7 , R 5 is positioned para to the same, and vice versa. or
  • K is a coupling component of the following general formulae (K4) to (K6);
  • T is a reactive anchor of general formulae (T1) to (T3);
  • R 24 and R 25 independent from one another are halogen or
  • R to R independent from one another are halogen
  • each of R 24 to R 30 independent from one another are substituted by one of the groups selected from general formulae (1 a) to (1 c);
  • R 31 , R 32 , R 339 and R 340 are hydrogen, alkyl, phenyl or phenyl substituted by one of the groups selected from alkyl, alkoxy, halogen, or -SOsM; alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, ⁇ , ⁇ -dicycloalkyl-carbamoyl, N,N- dialkyl-carbamoyl, N-monoaryl-carbamoyl, ⁇ , ⁇ -diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-
  • R 33 , R 34 and R 338 are hydrogen, alkyl, alkoxyl, halogen, trifluoromethyl, cyano, nitro, ester, carbamoyl, SO 3 M or-S0 2 X;
  • M is hydrogen, sodium, potassium, lithium or ammonium
  • X is vinyl or a radical -CH 2 CH 2 -Y where Y is a group removable under alkaline conditions such as OSO 3 M, SSO 3 M, OCOCH 3 , OPO 3 M or halogen; p is an integer from 1 to 5 R 13 and R 15 , independent from each other, are hydrogen, alkyl, cycloalkyl,
  • R 12 , R 16 and R 22 independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SO 3 M;
  • R 14 , R 17 to R 20 and R 23 are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, ⁇ , ⁇ -dicycloalkyl-carbamoyl, N,N- dialkyl-carbamoyl, N-monoaryl-carbamoyl, ⁇ , ⁇ -diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicyclo
  • R 21 is hydroxyl or amino group
  • the point of attachment and R 16 can be positioned ortho or para to the amino rest bearing the substituents R 17 and R 18 , meaning that when the point of attachment is positioned ortho to amino rest bearing the substituents R 17 and R 18 , R 16 is positioned para to the same, and vice versa.
  • A is the phenylene or napthylene middle component and has the general formula (A1 ) or (A2);
  • R 341 to R 348 are hydrogen, alkyl, alkyl chain interrupted by one or two heteroatoms, alkoxy, halogen, trifluoromethyl; cycloalkyl;
  • heterocycloalkyl cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, alkylureido, S0 3 M, COOM;
  • alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;
  • R its and R independent from each other are, hydrogen, alkyl, alkyl substituted by SO3M, alkyl chain interrupted by one or two heteroatoms, or T;
  • U is -0-, -S- or -N(R 329 )-;
  • R 323 , R 327 and R 329 are hydrogen, alkyl, alkyl substituted by SO 3 M, alkyl chain interrupted by one or two heteroatoms;
  • R 324 , R 325 , R 326 and R 328 are hydrogen, alkyl or alkyl chain interrupted by one or two heteroatoms;
  • r is an integer of 0 to 6;
  • s is an integer of 1 to 6;
  • T has the meaning as above;
  • B is the diazo component and has one of the general formula (B1 ) or (B2);
  • R to R and R independent from one another, are hydrogen or alkyi, alkoxy, halogen, cyano, -S0 3 M, trifluoromethyl, nitro, ester, NHC(0)R 41 , CONH 2 , S(0) 2 R 4 SO 2 X or aminosubstituted by T or one of the general formulae (E1 ) to (E3);
  • V is -0-, -S- or -N(R 352 )-
  • R 43 , R 47 and R 352 independent from one another, are hydrogen, alkyi, alkyi substituted by S0 3 M, alkyi chain interrupted by one or two heteroatoms;
  • R 44 , R 45 , R 46 and R 48 independent from one another, are hydrogen, alkyl or alkyl chain interrupted by one or two heteroatoms;
  • R 330 to R 333 are hydrogen or alkyl, alkoxy, halogen, cyano, -S0 3 M, trifluoromethyl, nitro, ester, NHC(0)R 334 , CONH 2 , S(0) 2 R 335 or a group of formula (3a);
  • R 336 and R 337 are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, ⁇ , ⁇ -dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, ⁇ , ⁇ -diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulf
  • R 41 , R 42 , R 334 and R 335 independent from one another are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;
  • c is an integer of 0 to 6;
  • d is an integer of 1 to 6;
  • T and X are the same as defined above;
  • M is hydrogen, lithium, sodium, potassium, ammonium or mono-, di-, tri- or tetra-(Ci- C 4 )-alkylammonium, one equivalent of an alkali earth metal, or a monovalent organic cation;
  • the dyes of general formula (I) contain at least one reactive anchor.
  • Alkyl groups appearing in this application may be straight-chain or branched, may have 1 to 12 C-atoms and are for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n- nonyl, n-decyl, n-undecyl and n-dodecyl, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl,
  • Cycloalkyl groups are (C 3 -C 8 )-cycloalkyl groups, preferably (C -C 8 )-cycloalkyl, particularly preferred cyclopentyl and cyclohexyl.
  • the term cyloalkyi comprises for the purpose of the present application substituted cycloalklyl groups and unsatured cycloalkyl groups as well.
  • a preferred group of this type is cyclopentenyl.
  • Preferred substituents are alkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, -S0 3 M, -COOM, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl- mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido,
  • alkenyl groups may be straight-chain or branched and are for example vinyl and allyl.
  • alkenyl comprises for the purpose of the present application alkynyl groups as well, for example ethynyl and propargyl.
  • Heterocycloalkyl groups are preferably pyrrolidine, piperidine, morpholine or
  • Aryl groups appearing in this application are phenyl or naphthyl.
  • the terms phenyl and naphthyl comprises unsubstituted as well as substituted phenyl and naphthyl.
  • Preferred substituents are alkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, -SO 3 M, -COOM, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl- mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido,
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine and particularly preferred chlorine and bromine
  • Preferred embodiments of the present invention are dyes of the formulae (la) to (If) and mixtures thereof;
  • R 49 , R 58 , R 66 , R 74 , R 78 and R 85 are hydrogen, alkyl, cycloalkyi, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino; monoaryl-amino; diaryl-amino; monocycloalkyl monoarylamino; monoalkyi monoaryl amino; alkylthio; arylthio; or
  • R 50 , R 54 , R 59 , R 67 , R 75 and R 79 independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - S0 3 M;
  • R 51 , R 55 , R 60 and R 68 independent from each other, are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, ⁇ , ⁇ -dicycloalkyl-carbamoyl, N,N- dialkyl-carbamoyl, N-monoaryl-carbamoyl, ⁇ , ⁇ -diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyi, N-monoalkyl-sulfamoyi, N-monoalky
  • R 52 , R 53 , R 56 , R 57 , R 64 , R 65 , R 72 , R 73 , R 76 , R 77 , R 83 and R 84 are hydrogen or alkyl, alkoxy, halogen, cyano, -SO 3 M, trifluoromethyl, nitro, ester, NHC(0)R 86 , CONH 2 , S(0) 2 R 87 or -S0 2 X;
  • R 86 and R 87 independent from one another are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;
  • R 61 to R 63 , R 69 to R 71 and R 80 to R 82 are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen, trifluoromethyl; cycloalkyl; heterocycloalkyl; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyi, ureido, alkylureido, SO 3 M, COOM; or a group of formulae (2a) to (2c) as defined above; In the especially preferred dyes of the present invention,
  • R 49 , R 58 , R 66 , R 74 , R 78 and R 85 are hydrogen or (d-C 4 )-alkyl or aryl;
  • R 50 , R 54 , R 59 , R 67 , R 75 and R 79 are cyano, carbamido, alkoxy carbonyl, carbonyl, sulfomethyl, -SO 3 M or -COOM;
  • R 51 , R 55 , R 60 and R 68 are alkyl or aryl; Aryl substituted by one more substituents selected from alkyl, alkoxy, halogen or -SO 3 M;
  • R 61 to R 63 , R 69 to R 71 and R 80 toR 82 are hydrogen, (Ci- C )-alkyl, (Ci-C )-alkoxyl, hydroxyl, carbamido, halogen or -SO 3 M or contain group of formulae (2a) to (2c);
  • R 86 and R 87 independent from one another are hydrogen, alkyl or alkyl substituted by hydroxyl;
  • R 88 and R 89 independent fro each other are hydrogen, alkyl, alkyl substituted by SO 3 M; T, X and M are the same as defined above.
  • R 90 and R 94 are hydrogen, alkyl, cycloalkyl, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino; monoaryl-amino; diaryl-amino; monocycloalkyl monoarylamino; monoalkyl monoaryl amino; alkylthio; arylthio;
  • R 91 and R 95 independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -SOsM;
  • D 1 and D 2 independent from each other, are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N-monocycloalkyl- carbamoyl, N-monoalkyl-carbamoyl, ⁇ , ⁇ -dicycloalkyl-carbamoyl, N,N-dialkyl- carbamoyl, N-monoaryl-carbamoyl, ⁇ , ⁇ -diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoy
  • R 92 , R 93 , R 99 and R 100 are hydrogen or alkyl, alkoxy, halogen, cyano, -SO 3 M, trifluoromethyl, nitro, ester, NHC(0)R 101 , CONH 2 , S(0) 2 R 102 or
  • R 101 and R 102 independent from one another are hydrogen, alkyl or alkyl substituted by hydroxy or halogen.
  • R 96 to R 98 are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted,
  • halogen trifluoromethyl; cycloalkyl; heterocycloalkyl; cyano; nitro; acyloxy;
  • alkylcarbonyl acylamino
  • aryloylamino cinnamoylamino
  • alkylsulfonylamino alkylthio
  • alkylsulfonyl alkoxycarbonyl, carbamoyl, sulfamoyi, ureido, alkylureido, S0 3 M, COOM; or a group of formulae (2a) to (2c) as defined above;
  • T and M are the same as defined above;
  • R 90 and R 94 indenpendently, is hydrogen or (Ci-C 4 )-alkyl or aryl;
  • R 91 and R 95 indenpendently, is cyano, carbamido, alkoxy carbonyl, carbonyl, sulfomethyl, -SO 3 M or -COOM;
  • D 1 and D 2 independently, is alkyl or aryl; alkyl or aryl substituted by one more substituents selected from alkyl, alkoxy, halogen or -SOsM, amino, N-alkyl amino; R 96 to R 98 , independent from one another are hydrogen, (Ci-C 4 )-alkyl, (Ci-C 4 )-alkoxyl, hydroxyl, carbamido, halogen or -SOsM or contain group of formulae (2a) to (2c); R 101 and R 102 independent from one another are hydrogen, alkyl or alkyl substituted by hydroxyl;
  • T, X and M are the same as defined above.
  • R 105 , R 110 , R 115 and R 123 are hydrogen, alkyl, cycloalkyl, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino;
  • R 106 , R 111 , R 116 and R 124 independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - S0 3 M;
  • R 107 , R 112 , R 117 and R 125 are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, ⁇ , ⁇ -dicycloalkyl-carbamoyl, N,N- dialkyl-carbamoyl, N-monoaryl-carbamoyl, ⁇ , ⁇ -diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,
  • R 108 , R 109 , R 113 , R 114 , R 121 , R 122 , R 129 and R 130 are hydrogen or alkyl, alkoxy, halogen, cyano, -SO 3 M, trifluoromethyl, nitro, ester,
  • R 131 and R 132 are hydrogen, alkyl or alkyl substituted by hydroxy or halogen.
  • en t f rom one another are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen ,trifluoromethyl; cycloalkyi; heterocycloalkyi; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyi, ureido, alkylureido, S0 3 M, COOM; or a group of formulae (2a) to (2c);
  • E 4 to E 7 independent from each other, are a group of general formulae (E1 ) - (E3);
  • R 105 , R 110 , R 115 and R 123 independent from each other are hydrogen or (Ci-C 4 )-alkyl or aryl;
  • R 106 , R 111 , R 116 and R 124 independent from each other are cyano, carbamido, alkoxy carbonyl, carbonyl, sulfomethyl, -SO 3 M or -COOM;
  • R 107 , R 112 , R 117 and R 125 independent from each other are alkyl or aryl; Aryl substituted by one more substituents selected from alkyl, alkoxy, halogen or -SOsM;
  • en t f rom one another are hydrogen, (C 1 -C 4 )- alkyl, (Ci-C 4 )-alkoxyl, hydroxyl, carbamido, halogen or -SO3M or contain group of formulae (2a) to (2c);
  • R 108 , R 109 , R 113 , R 114 , R 121 , R 122 , R 129 and R 130 independent from one another are hydrogen or alkyl, alkoxy, halogen, -SO 3 M or -SO 2 X;
  • R 131 and R 132 independent from one another are hydrogen, alkyl or alkyl substituted by hydroxyl;
  • E 4 to E 7 independent from each other, are a group of general formulae (E1 ) to (E3); T, X and M are the same as defined above. Further preferred emodiment of the present invention are dyes of the formulae (Im) to (Ip) and mixtures thereof;
  • R 135 , R 139 , R 143 and R 150 are hydrogen, alkyl, cycloalkyl, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino;
  • R 136 , R 140 , R 144 and R 151 are alkyl substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido or phenylureido; R 136 , R 140 , R 144 and R 151 , independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - S0 3 M
  • D 3 , D 4 , D 5 and D 6 independent from each other, are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, N- monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, ⁇ , ⁇ -dicycloalkyl-carbamoyl, N,N- dialkyl-carbamoyl, N-monoaryl-carbamoyl, ⁇ , ⁇ -diaryl-carbamoyl, N-monocycloalkyl-N- monoarylcarbamoyl, N-monoalkyl-N-monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl- sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicyclo
  • alkyl interrupted by one or more heteroatoms such as oxygen or sulfur;
  • R 137 , R 138 , R 141 , R 142 , R 148 , R 149 , R 155 and R 156 are hydrogen or alkyl, alkoxy, halogen, cyano, -SO 3 M, trifluoromethyl, nitro, ester,
  • R 157 and R 158 are hydrogen, alkyl or alkyl substituted by hydroxy or halogen.
  • R 145 , R 146 , R 147 , R 152 , R 153 and R 154 are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen ,trifluoromethyl; cycloalkyi; heterocycloalkyi; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyi, ureido, alkylureido, S0 3 M, COOM; or contain a group of formulae (2a) to (2c) as defined above;
  • E 8 to E 11 independent from each other, are a group of general formulae (E1 ) to (E3) as defined above;
  • T, X and M are the same as defined above.
  • R 135 , R 139 , R 143 and R 150 independent from each other are hydrogen or (Ci-C 4 )-alkyl or aryl;
  • R 136 , R 140 , R 144 and R 151 independent from each other are cyano, carbamido, alkoxy carbonyl, carbonyl, sulfomethyl, -SO 3 M or -COOM;
  • D 3 , D 4 , D 5 and D 6 independent from each other are alkyl or aryl; alkyl or aryl
  • R 137 , R 138 , R 141 , R 142 , R 148 , R 149 , R 155 and R 156 independent from one another are hydrogen or alkyl, alkoxy, halogen, -SO 3 M or -SO 2 X;
  • R 145 to R 147 and R 152 to R 154 are hydrogen, (Ci-C 4 )- alkyl, (Ci-C )-alkoxyl, hydroxyl, carbamido, halogen or -SO 3 M or contain group of formulae (2a) to (2c);
  • E 8 to E 11 independent from each other, are a group of general formulae (E1 ) to (E3); T, X and M are the same as defined above.
  • each of R 161 , R 168 , R 175 and R 185 are alkyl, cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or -S0 3 M;
  • R 162 , R 169 , R 176 and R 186 independent from each other are hydroxyl or amino;
  • heterocycloalkyl carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, ⁇ , ⁇ -dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N- monoarylcarbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, ⁇ , ⁇ -dicycloalkylsulfamoyl, ⁇ , ⁇ -dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-
  • alkyl or aryl substituted by -SO 2 X whereby X is vinyl or a radical -CH 2 CH 2 -Y where Y is a group removable under alkaline conditions such as OSO 3 M; or a rest with free valence to link to reactive anchor T;
  • R 166 , R 167 , R 173 , R 174 , R 183 , R 184 , R 193 and R 194 are hydrogen or alkyl, alkoxy, halogen, cyano, -SO 3 M, trifluoromethyl, nitro, ester,
  • NHC(0)R 195 CONH2, S(0) 2 R 196 or -S0 2 X;
  • R 195 and R 196 independent from one another, are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;
  • en t f rom one another are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen ,trifluoromethyl; cycloalkyl; heterocycloalkyl; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, alkylureido, S0 3 M, COOM; or contain a group of formulae (2a) to (2c);
  • X is the same as defined above.
  • R 161 , R 168 , R 175 and R 185 are (Ci-C 4 )-alkyl, cyano, carbamido, alkoxy carbonyl, carbonyl or sulfomethyl;
  • R 162 , R 169 , R 176 and R 186 are hydroxyl or amino
  • R 163 to R 165 , R 170 to R 172 , R 177 to R 179 and R 187 to R 189 , are independent from one another are hydrogen, (Ci-C )-alkyl, (Ci-C )-alkyloxy, halogen, -S0 3 M or -S0 2 X or free valence substituted with T;
  • R 166 , R 167 , R 173 , R 174 , R 183 , R 184 , R 193 and R 194 independent from one another are hydrogen, (Ci-C )-alkyl, (Ci-C )-alkoxyl, halogen or -S0 3 M;
  • R 180 to R 182 and R 190 to R 192 are hydrogen, (Ci-C 4 )- alkyl, (Ci-C 4 )-alkoxyl, hydroxyl, carbamido, halogen or -S0 3 M or contain the group of formulae (2a) to (2c);
  • T, X and M have the same meaning as above.
  • Further preferred embodiments of the present invention are dyes of the formulae (lu) to (Ix) and mixtures thereof;
  • R 199 , R 206 , R 213 and R 223 independent from each other, are alkyl, cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - SO 3 M;
  • R 200 , R 207 , R 214 and R 224 independent from each other are hydroxyl or amino;
  • R 215 tQ r 217 and R 225 fo R 227 > j ndepenc
  • en t f rom each other are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl,
  • heterocycloalkyl carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, ⁇ , ⁇ -dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N- monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, ⁇ , ⁇ -dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-
  • X is vinyl or a radical -CH 2 CH 2 -Y where Y is a group removable under alkaline conditions such as OSO 3 M; or contains a rest with free valence to link to rest reactive anchor T;
  • R 204 , R 205 , R 211 , R 212 , R 221 , R 222 , R 231 and R 232 independent from one another are hydrogen or alkyl, alkoxy, halogen, cyano, -SO 3 M, trifluorom ethyl, nitro, ester,
  • NHC(0)R 233 CONH2, S(0) 2 R 234 or -S0 2 X;
  • R 233 and R 234 independent from one another are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;
  • R 218 to R 220 and R 228 to R 230 are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen ,trifluoromethyl; cycloalkyi; heterocycloalkyi; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, alkylureido, SO 3 M, COOM; or a group of formulae (2a) to (2c) as defined above;
  • E 12 to E 15 are a group of general formulae (E1 ) to (E3) as defined above;
  • T, X and M have the same meanings as above.
  • R 199 , R 206 , R 213 and R 223 independent from each other are (Ci-C 4 )-alkyl, cyano, carbamido, alkoxy carbonyl, carbonyl or sulfomethyl;
  • R 200 , R 207 , R 214 and R 224 independent from each other are hydroxyl or amino;
  • R 201 tQ R 203 ⁇ R 208 tQ R 210 j R 215 ⁇ q r 217 R 225 ⁇ q r 227 ⁇ j ndependent from Qne an0 ther, are hydrogen, (Ci-C )-alkyl, (Ci-C )-alkyloxy, halogen, -SO 3 M or -S0 2 X or free valence substituted with T;
  • R 204 , R 205 , R 211 , R 212 , R 221 , R 222 , R 231 and R 232 , independent from one another are hydrogen, (Ci-C )-alkyl, (Ci-C )-alkoxyl, halogen or -S0 3 M;
  • R218 10 R 22o and R 228 to R 230 independent from one another are hydrogen, (C 1 -C 4 )- alkyl, (Ci-C 4 )-alkoxyl, hydroxyl, carbamido, halogen or -SOsM or contain the group of formulae (2a) to (2c);
  • E 12 to E 15 independent from each other, are a group of general formulae (E1 ) to (E3); T and X have the same meanings as above.
  • R 237 , R 245 , R 253 and R 264 independent from each other, are hydrogen, alkyl, cycloalkyl, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino;
  • R 238 , R 246 , R 254 and R 265 independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - S0 3 M;
  • en t f r0 m each Other are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl,
  • heterocycloalkyl carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, ⁇ , ⁇ -dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N- monoarylcarbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, ⁇ , ⁇ -dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-
  • NHC(0)R 276 CONH2, S(0) 2 R 277 or -S0 2 X;
  • R 276 and R 277 are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;
  • R 259 to R 261 and R 271 to R 273 are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen ,trifluoromethyl; cycloalkyi; heterocycloalkyi; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyi, ureido, alkylureido, S0 3 M, COOM; or contain a group of formulae (2a) to (2c) as defined above; In the especially preferred dyes of the formulae (ly) to (lab),
  • R 237 , R 245 , R 253 and R 264 are hydrogen or (Ci-C 4 )-alkyl, aryl, (Ci-C 4 )-alkyloxy;
  • R 238 , R 246 , R 254 and R 265 are (Ci-C 4 )-alkyl, cyano, carbamido, alkoxy carbonyl, carbonyl or sulfomethyl;
  • R 239 tQ R 242 ⁇ R 247 ⁇ q r 250 ⁇ R 255 ⁇ q r 258 ⁇ R 267 ⁇ q r 270 ⁇ j ndependent from Qne an0 ther, are hydrogen, (Ci-C )-alkyl, (Ci-C 6 )-alkyloxy, aryl;
  • R 243 , R 244 , R 251 , R 252 , R 262 , R 263 , R 274 and R 275 are hydrogen, (Ci-C 4 )-alkyl, (Ci-C 4 )-alkoxyl, halogen or -S0 3 M;
  • R 259 to R 261 and R 271 to R 273 independent from one another, are hydrogen, (C 1 -C4)- alkyl, (Ci-C 4 )-alkoxyl, hydroxyl, carbamido, halogen or -SOsM or contain the group of formulae (2a) to (2c);
  • T, X and M have the same meanings as defined above.
  • R , R , R and R independent from each other, are hydrogen, alkyl, cycloalkyl, trifluoromethyl; alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino; hydroxyl, monocycloalkyl-amino; monoalkyl-amino; di(cyclo)alkyl-amino; dialkyl-amino;
  • R 281 , R 289 , R 297 and R 308 independent from each other, are cyano, carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl, halogen, methyl sulfonyl or - SO 3 M;
  • R 309 ⁇ q R 312 j ndependent from egch other> are hydrogen, alkyl, alkenyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl,
  • heterocycloalkyl carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, ⁇ , ⁇ -dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl- carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N- monoarylcarbamoyl, sulfamoyi, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl, N,N-dicycloalkylsulfamoyl, ⁇ , ⁇ -dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-
  • NHC(0)R 318 CONH2, S(0) 2 R 319 or -S0 2 X;
  • R 318 and R 319 are hydrogen, alkyl or alkyl substituted by hydroxy or halogen;
  • R 302 to R 304 and R 313 to R 315 are hydrogen, alkyl, alkyl substituted, alkyl chain interrupted by one or two heteroatoms, alkoxy, alkoxy substituted, halogen ,trifluoromethyl; cycloalkyi; heterocycloalkyi; cyano; nitro; acyloxy; alkylcarbonyl, acylamino; aryloylamino, cinnamoylamino, alkylsulfonylamino; alkylthio; alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, alkylureido, SO3M, COOM or contain a group of formulae (2a) to (2c) as defined above;
  • E 16 to E 19 independent from each other, are a group of general formulae (E1 ) to (E3) as defined above;
  • T, X and M have the same meanings as defined above.
  • R 280 , R 288 , R 296 and R 307 independent from each other are hydrogen or (d-C 4 )-alkyl, aryl, (Ci-C )-alkyloxy;
  • R 281 , R 289 , R 297 and R 308 independent from each other are (Ci-C 4 )-alkyl, cyano, carbamido, alkoxy carbonyl, carbonyl or sulfomethyl;
  • R 282 to R 285 , R 290 to R 293 , R 298 to R 301 and R 309 to R 311 , independent from one another, are hydrogen, (Ci-C )-alkyl, (Ci-C 6 )-alkyloxy, aryl;
  • R 286 , R 287 , R 294 , R 295 , R 305 , R 306 , R 316 and R 317 are hydrogen, (Ci-C )-alkyl, (Ci-C )-alkoxyl, halogen or -S0 3 M;
  • en t f rom one another are hydrogen, (C 1 -C 4 )- alkyl, (Ci-C 4 )-alkoxyl, hydroxyl, carbamido, halogen or -S0 3 M or contain the group of formulae (2a) to (2c);
  • E 16 to E 19 independent from each other, are a group of general formulae (E1 ) to (E3); T, X and M are the same as defined above.
  • Examples of the preferred dyes of this invention are the dyes from 1 to 168 (Table 1 ) corresponding to the general formula (II).
  • K 7 is a radical of heterocyclic coupling component and has the same meaning as described above for K;
  • a 3 is a radical of middle component and has the same meaning as described above for A;
  • B 3 is a radical of diazo component and has the same meaning as described above for B;
  • M is hydrogen, sodium, potassium, lithium or ammonium;
  • K 8 is a radical of heterocyclic coupling component and has the same meaning as described above for K;
  • a 4 is a radical of middle component and has the same meaning as described above for A;
  • B 4 is a radical of diazo component and has the same meaning as described above for B;
  • M is hydrogen, sodium, potassium, lithium or ammonium;
  • the present invention also provides a process for the preparation of the dyes of the formula (I) which comprises diazotization of the compounds of the formulae (IV) and reacting the correspondingly obtained diazonium salts with a compound of the formula K to obtain the intermediate of general formula (V).
  • the diazo component (B-NH 2 ) is diazotised and coupled onto the intermediate V to obtain the bisazo of eneral formula (VI).
  • the diazo component (B-NH 2 ) can be diazotised and coupled onto the compound (A-NH 2 ) to obtain intermediate (VII). Further, the intermediate (VII) is diazotised and coupled onto compound (V) to obtain the trisazo dye of general formula (VIII).
  • the dyes (VI) and (VIII) are reacted with copper salt especially copper sulphate to obtain the copper complex dyes (IX) and (X).
  • the diazotization of the compounds of the formulae (IV), B-NH 2 and (VII) can be performed by means of diazotization methods that are known to a person skilled in the art, preferably by using sodium nitrite or nitrosylsulfuric acid in acidic medium using inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereof or organic acids such as acetic acid or propionic acid or mixtures thereof. Also mixtures of inorganic acid with organic acids can be advantageously used.
  • the coupling reaction of the diazotized compounds of the formulae (IV), B-Nh and (VII) onto the compound of formula (K) and (V) can likewise be performed by known methods.
  • the complexation reaction of the dyes (VI) and (VIII) can likewise be performed by known methods.
  • the compounds of the formula A, B and K are known and commercially available or can be synthesised by means of common chemical reactions known to a person skilled in the art.
  • the present invention also provides for the use of the present invention's dyes for dyeing or printing of hydroxyl-, amino-, and/or carboxamido-containing material, or a process for dyeing or printing of hydroxyl- and/or carboxamido-containing material whereby a dye is applied to the material and fixed on the material by usual means, the process utilizing a dye in accordance with the present invention.
  • Hydroxyl-containing materials can be of natural or synthetic origin. Examples are cellulose fiber materials, preferably cotton, linen, hemp, jute and ramie fibers, regenerated cellulose fibers such as preferably staple viscose and filament viscose, chemically modified cellulose fibers, such as for example aminated cellulose fibers, and also polyvinyl alcohols.
  • Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-1 1 and nylon-4.
  • the hydroxyl- and/or carboxamido-containing materials mentioned can be present in various forms.
  • sheetlike structures such as paper and leather
  • films such as nylon films
  • a bulk mass for example composed of polyamide and polyurethane
  • fibers for example cellulose fibers.
  • the fibers are preferably textile fibers, for example in the form of woven fabrics or yarns or in the form of hanks or wound packages.
  • the dyes of the present invention and their salts or mixtures can be used as a single dyeing product in dyeing or printing processes or it can be part of a di/tri or multi- component combination product in dyeing or in printing compositions.
  • Dyes of this invention and their salts or mixtures are highly compatible with other known and/or commercially available dyes and they can be used together with such dyes to obtain specific hues of similarly good technical performance.
  • Technical performance includes build-up, fastness properties and levelness.
  • the dyes according to the invention can be applied to the materials mentioned, especially the fiber materials mentioned, by the application techniques known for water-soluble dyes. This applies to both, dyeing and printing processes.
  • the material to be dyed is introduced into the bath at a temperature of about 40°C, agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature between 60 and 98°C.
  • the dyeings can also be carried out at the boil or in sealed dyeing apparatus at temperatures of up to 106°C.
  • the water solubility of the dyes according to the invention is very good, they can also be used with advantage in customary continuous dyeing processes.
  • the dyes of the present invention can also be used in digital printing processes, in particular in digital textile printing.
  • the dyes of the present invention need to be formulated in inks.
  • Aqueous inks for digital printing which comprise a dye in
  • the inks of the present invention comprise the dye of the present invention in amounts which preferably range from 0.1 % by weight to 50% by weight, more preferably from 1 % by weight to 30% by weight and most preferably from 1 % by weight to 15% by weight, based on the total weight of the ink.
  • the inks, as well as the dye of the present invention, may if desired contain further dyes used in digital printing.
  • a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte.
  • Useful electrolytes include for example lithium nitrate and potassium nitrate.
  • the inks of the present invention may include organic solvents at a total level of 1 -50% and preferably 5-30% by weight.
  • Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1 -propanol, isopropanol, 1 -butanol, tert-butanol, pentyl alcohol, polyhydric alcohols for example: 1 ,2-ethanediol, 1 ,2,3-propanetriol, butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,2-propanediol, 2,3-propanediol, pentanediol, 1 ,4-pentanediol, 1 ,5- pentanediol, hexanediol, D,L-1 ,2-hexanediol, 1 ,6-hexanediol, 1 ,2,6-hexanetriol, 1 ,2- octanediol, polyalkylene
  • polypropylene glycol glycerol ether polyethylene glycol tridecyl ether, polyethylene glycol nonylphenyl ether, amines, such as for example: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine,
  • the inks of the invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1.5 to 40.0 mPas in a temperature range from 20 to 50°C.
  • Preferred inks have a viscosity of 1.5 to 20 mPas and particularly preferred inks have a viscosity of 1 .5 to 15 mPas.
  • Useful viscosity moderators include rheological additives, for example:
  • polyvinylcaprolactam polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified
  • galactomannans polyetherurea, polyurethane, nonionic cellulose ethers.
  • the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mN/m, which are adapted if necessary as a function of the process used (thermal or piezo technology).
  • Useful surface-active substances include for example: all surfactants, preferably nonionic surfactants, butyldiglycol, 1 ,2- hexanediol.
  • the inks of the present invention may further include customary additives, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1 % by weight based on the total weight of the ink.
  • the inks may be prepared in a conventional manner by mixing the components in water.
  • the inks of the invention are particularly useful in inkjet printing processes for printing a wide variety of pretreated materials, such as silk, leather, wool, polyamide fibers and polyurethanes, and cellulosic fiber materials of any kind.
  • Blend fabrics for example blends of cotton, silk, wool with polyester fibers or polyamide fibers can similarly be printed.
  • auxiliaries have to be applied to the textile substrate in a separate pretreatment step.
  • the pretreatment of the textile substrate is effected with an aqueous alkaline liquor prior to printing.
  • thickeners to prevent flowing of the motives when the printing ink is applied, for example sodium alginates, modified polyacrylates or highly etherified galactomannans.
  • These pretreatment reagents are uniformly applied to the textile substrate in a defined amount using suitable applicators, for example using a 2- or 3-roll pad, contactless spraying technologies, by means of foam application or using appropriately adapted inkjet technologies, and subsequently dried.
  • suitable applicators for example using a 2- or 3-roll pad, contactless spraying technologies, by means of foam application or using appropriately adapted inkjet technologies, and subsequently dried.
  • the examples below serve to illustrate the invention. Parts and percentages are by weight unless noted otherwise. The relationship between parts by weight and parts by volume is that of the kilogram to the liter.
  • 1 part of the dye of the formula (I) was dissolved in 2000 parts of water and 1 part of a leveling agent (based on a condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate were added. The pH was then adjusted to 5 using acetic acid (80%). The dye bath was heated to 50 °C. for 10 minutes and then entered with 100 parts of a woven polyamide fabric. The temperature was raised to 1 10 °C. over the course of 50 minutes and then dyeing was lowered by cooling to 60 °C. and the dyed material was removed. The polyamide fabric was washed with hot and cold water, soaped and spun dried.
  • a leveling agent based on a condensation product of a higher aliphatic amine and ethylene oxide
  • a textile fabric consisting of mercerized cotton was padded with a liquor containing 35g/l of calcium sodium carbonate, 100 g/l of urea and 150 g/l of a low-viscosity sodium alginate solution (6%), and then dried.
  • the liquor pickup was 70%.
  • the textile thus pretreated was printed with an aqueous ink containing 2% of the dye of example (I), 20% of sulfolane, 0.01 % of Mergal K9N and 77.99% of water using a drop-on- demand (bubblejet) ink-jet printing head.
  • the print was fully dried. It was fixed by means of saturated steam at 102 °C for 8 minutes.
  • the print was then rinsed warm, subjected to a fastness wash with hot water at 95 °C. Again rinsed with warm water and then dried.

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  • Chemical & Material Sciences (AREA)
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  • Plural Heterocyclic Compounds (AREA)
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Abstract

La présente invention concerne des colorants de formule (I) et des mélanges de ceux-ci, dans laquelle n, A, B et K sont tels que définis la revendication, leur procédé de préparation et leur utilisation pour la coloration et l'impression de matériaux contenant des groupes hydroxyles, amines, et/ou carboxamides.
EP13731709.5A 2012-06-18 2013-06-13 Colorants réactifs et leurs complexes métalliques, leur procédé de production et leur utilisation Withdrawn EP2904142A1 (fr)

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KR20150032668A (ko) 2015-03-27
WO2013189816A1 (fr) 2013-12-27
JP2015525280A (ja) 2015-09-03
MX2014015534A (es) 2015-07-17
AU2013279555A1 (en) 2014-11-06

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