US20060229440A1 - Disazo dyes, and copper complexes thereof, for dyeing paper - Google Patents

Disazo dyes, and copper complexes thereof, for dyeing paper Download PDF

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US20060229440A1
US20060229440A1 US11/446,848 US44684806A US2006229440A1 US 20060229440 A1 US20060229440 A1 US 20060229440A1 US 44684806 A US44684806 A US 44684806A US 2006229440 A1 US2006229440 A1 US 2006229440A1
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alkyl
hydrogen
alkoxy
hydroxy
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Adolf Kaser
Holger Lautenbach
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    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0055—Mixtures of two or more disazo 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
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02—Disazo dyes
    • C09B35/021—Disazo dyes characterised by two coupling components of the same type
    • C09B35/027—Disazo dyes characterised by two coupling components of the same type in which the coupling component is a hydroxy-amino compound
    • C09B35/029—Amino naphthol
    • 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
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02—Disazo dyes
    • C09B35/039—Disazo dyes characterised by the tetrazo component
    • 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
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/35—Trisazo dyes in which the tetrazo component is a diamino-azo-aryl compound
    • 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
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/24—Disazo or polyazo compounds
    • C09B45/28—Disazo or polyazo compounds containing copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/919—Paper

Definitions

  • the present invention relates to dyes of formula wherein
  • the present invention relates also to mono- or bis-copper complexes of dyes of formula wherein R 1 and/or R 3 are hydroxy or alkoxy and the other substituents are as defined for formula (1).
  • the dyes are shown in the form of the free acid, but the corresponding salts, for example metal or ammonium salts, are also to be included.
  • X is preferably azo, azoxy or —C ⁇ C—.
  • halogen is generally fluorine, bromine or, especially, chlorine.
  • alkyl radicals are to be understood as being generally open-chain or branched or cyclic alkyl radicals, preferably containing from 1 to 8 carbon atoms, for example methyl, ethyl, n- or iso-propyl, n-, sec- or tert-butyl, n-hexyl, n-octyl, cyclopentyl and cyclohexyl.
  • Aryl is to be understood as being especially naphthyl or phenyl, each of which may be substituted by, for example, C 1 -C 4 alkyl, and more especially unsubstituted naphthyl or phenyl.
  • alkyl radicals and also the cycloalkyl or aryl groups may be mono- or poly-substituted, for example by hydroxy, carboxy, halogen, cyano, amino or C 1 -C 4 alkoxy.
  • the alkoxy radicals may have from 1 to 12 carbon atoms, preferably from 1 to 4 carbon atoms and are, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy and n-hexyloxy.
  • the alkoxy groups also may be substituted, for example by the radicals listed as possible substituents for the alkyl groups, especially by hydroxy or C 1 -C 4 alkoxy.
  • Z 2 is preferably hydrogen, hydroxy, alkoxy, amino, NH—COO—C 1 -C 4 alkyl, or anilino which is unsubstituted or substituted by amino and/or by sulfo.
  • Z 1 is preferably NH—COO—C 1 -C 4 alkyl or the 4-amino-3-sulfo-anilino radical.
  • R 2 and R 4 are preferably hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
  • Z 1 and Z 2 are identical and each is NH—COO—C 1 -C 4 alkyl or the 4-amino-3-sulfo-anilino radical.
  • the dyes of formula (1) are prepared in a manner known per se, for example a diamine of formula is tetraazotised in known manner and coupled with 2 moles of a coupling component of formula or with 1 mole each of a coupling component of formula (4) and a coupling component of formula under conditions known per se.
  • the corresponding compounds of formula (1) can also be prepared in a manner likewise known per se by diazotisation of unsubstituted or substituted p-nitroanilines, coupling with a coupling component of formula (4) and/or (5) and subsequent reduction, for example using glucose.
  • the dyes of formula (1) which contain a free amino group can, in many cases, be prepared in pure form only with difficulty. An improvement can be achieved by introducing a protecting group which is subsequently removed. That is the case especially for those dyes wherein X is azoxy.
  • Suitable protecting groups are those that are readily removable and that are stable under the conditions of the basic azoxy condensation.
  • An alkoxycarbonyl group, especially the ethoxycarbonyl group, is especially suitable.
  • the mono- or bis-copper complexes of dyes of formula (2) are obtained in a manner known per se by means of copper-treatment of the customarily prepared dyes of formula (1) using copper-yielding agents in amounts of from 1 to 2.5 moles of copper per mole of dye of formula (1).
  • the copper-treatment can also be carried out by demethylation as a result of cleavage of an alkoxy group or oxidatively with introduction of an additional oxygen group.
  • the invention preferably relates to the mono-copper complexes of dyes of formula (2) and mixtures thereof with the bis-copper complexes of such dyes.
  • one of the halves of the dye of formula (2) that are connected by X can be reacted with up to 1 mole of copper-yielding agent and then to be connected to the second, non-copper-treated half by a direct bond or via the bridging member X. It is preferred, however, to start from the dye of formula (2) and to react that dye with a copper-yielding agent.
  • the dyes of formula (1) and the mono- and bis-copper complexes of dyes of formula (2) are suitable for dyeing natural and synthetic material.
  • the material is, for example, fibre material of leather, wool, polyamide, glass fibres or cotton and, especially, paper.
  • the invention relates also to the use, for dyeing paper, of dyes of formula wherein
  • the dyes of formula (1) and the copper complexes of dyes of formula (2) or the mixtures of mono-copper complex with the bis-copper complex are preferably used as solid or liquid commercial forms.
  • the dyes are used especially in discontinuous mass dyeing, the dyes being added usually in the form of a stock solution to the pulper, hollander or mixing vat.
  • dye preparations are preferably used which may also comprise, besides the dye, diluents, e.g. urea as solubiliser, dextrin, Glauber's salt, sodium chloride and dispersants, dusting agents and sequestrants, such as tetrasodium phosphate.
  • the invention accordingly relates also to solid dye preparations for dyeing paper, which preparations comprise a dye of formula (1) according to the invention or a mono- or bis-copper complex of a dye of formula (2).
  • the invention accordingly relates also to concentrated aqueous solutions of the dyes of formula (1) used in accordance with the invention or of the mono- or bis-copper complexes of dyes of formula (2) for dyeing paper, which solutions contain from 5 to 30% by weight of dye, based on the total weight of the solution.
  • the concentrated solutions may comprise further auxiliaries, for example solubilisers, such as ⁇ -caprolactam or urea, organic solvents, such as glycols, polyethylene glycols, dimethyl sulfoxide, N-methylpyrrolidone, acetamide, alkanolamines or polyglycolamines.
  • solubilisers such as ⁇ -caprolactam or urea
  • organic solvents such as glycols, polyethylene glycols, dimethyl sulfoxide, N-methylpyrrolidone, acetamide, alkanolamines or polyglycolamines.
  • the pH is adjusted to 7.5 using 32% hydrochloric acid, with cooling, salted out with 60 parts of sodium chloride and filtered.
  • the dye of formula is obtained. It dyes cellulose fibres, especially paper, brilliant reddish-blue shades having good fastness properties and with a high degree of exhaustion.
  • Example Coupling Component 2 1-methoxycarbonylamino-8-naphthol-3,6-disulfonic acid 3 1-ethoxycarbonylamino-8-naphthol-2,4-disulfonic acid 4 1-ethoxycarbonylamino-8-naphthol-4,6-disulfonic acid 5 2-ethoxycarbonylamino-5-naphthol-1,7-disulfonic acid 6 3-ethoxycarbonylamino-5-naphthol-2,7-disulfonic acid 7 2-ethoxycarbonylamino-5-naphthol-7-sulfonic acid 8 3-ethoxycarbonylamino-5-naphthol-7-sulfonic acid 9 2-ethoxycarbonylamino-5-naphthol-4,8-dis
  • Example Diamine Coupling Component 13 4,4′-diamino-3,3′-dimethoxy- 1-ethoxycarbonylamino-8-naphthol-3,6- azobenzene disulfonic acid 14 4,4′-diamino-3,3′-dimethoxy- 1-methoxycarbonylamino-8-naphthol- azobenzene 3,6-disulfonic acid 15 4,4′-diamino-3,3′-dimethoxy- 3-ethoxycarbonylamino-5-naphthol-2,7- azobenzene disulfonic acid 16 4,4′-diamino-3,3′-dimethoxy- 2-ethoxycarbonylamino-5-naphthol-1,7- azobenzene disulfonic acid 17 4,4′-diamino-3,3′-dimethoxy- 2-ethoxycarbonylamino-5-naphthol-4,8-
  • the dyes described in Examples 28, 29, 40 and 41 are converted, in a manner known per se, into the mono-copper complexes, by means of “demethylating copper-treatment”. These complexes are especially suitable for dyeing paper with good fastness properties.
  • the dyes described in Examples 1-19, 38, 39 and 51-62 are converted, in a manner known per se, into the bis-copper complexes, by means of “demethylating copper-treatment”. These complexes are especially suitable for dyeing paper with good fastness properties.
  • the corresponding dyes having a free amino group can be obtained in analogous manner from the precursors described in Examples 3 to 10, 12, 13, 18, 19, 23, 25, 27, 29, 35, 37, 41, 44, 51, 56 and 57.

Abstract

The dyes of formula (1) according to claim 1 and the copper complexes of dyes of formula (2) according to claim 9 or the mixtures of mono-copper complex with the bis-copper complex are excellently suitable for dyeing paper with good light-fastness properties.

Description

  • This application is a divisional of U.S. Ser. No. 10/451,835, filed Jun. 25, 2003, now granted and incorporated herein entirely by reference.
  • The present invention relates to dyes of formula
    Figure US20060229440A1-20061012-C00001
    wherein
    • Z1 is NHR6,
    • R6 being a radical of formula CO—R8, CO—NH—R8, SO2-alkyl, SO2-aryl,
      Figure US20060229440A1-20061012-C00002
    •  COOR8,
    • R8 being hydrogen, alkyl or aryl and
    • R7 being COOH or SO3H in the o-position to the NH2 group,
    • Z2 is as defined for Z1 or is hydrogen, hydroxy, alkoxy or a radical NHR5,
    • R5 being hydrogen, alkyl, aryl, COR8, CO—NHR8 or SO2R8,
    • R1 and R3 are each independently of the other hydrogen, hydroxy, alkyl or alkoxy,
    • R2 and R4 are each independently of the other hydrogen, hydroxy, alkyl or alkoxy, halogen, sulfo, carboxy, NHCONHR8 or NHCOR8,
    • X is a direct bond in which case symmetrical compounds wherein Z1 and Z2 are NHCOCH3, NHCOOCH3 or NHCO-phenyl are excluded, or is —C═C— in which case both Z1 and Z2 cannot simultaneously be acetylamino, benzoylamino or 4-amino-3-sulfo-anilino, or is azo, azoxy, —NR8, —NR8CONR9— or a group of formula
      Figure US20060229440A1-20061012-C00003
    • Y being hydroxy, alkoxy or NR9R10,
    • R9 and R10 being each independently of the other hydrogen, unsubstituted or substituted alkyl or unsubstituted or substituted aryl,
    • n and m are each independently of the other 1 or 2,
      and wherein the rings A and B may each independently of the other carry a fused-on benzene ring,
      with the proviso that the compounds of formulae
      Figure US20060229440A1-20061012-C00004
      are excluded.
  • The present invention relates also to mono- or bis-copper complexes of dyes of formula
    Figure US20060229440A1-20061012-C00005
    wherein R1 and/or R3 are hydroxy or alkoxy and the other substituents are as defined for formula (1).
  • In this Application, the dyes are shown in the form of the free acid, but the corresponding salts, for example metal or ammonium salts, are also to be included.
  • In the dyes of formula (1), X is preferably azo, azoxy or —C═C—.
  • In this Application, halogen is generally fluorine, bromine or, especially, chlorine.
  • According to the invention, alkyl radicals are to be understood as being generally open-chain or branched or cyclic alkyl radicals, preferably containing from 1 to 8 carbon atoms, for example methyl, ethyl, n- or iso-propyl, n-, sec- or tert-butyl, n-hexyl, n-octyl, cyclopentyl and cyclohexyl.
  • Aryl is to be understood as being especially naphthyl or phenyl, each of which may be substituted by, for example, C1-C4alkyl, and more especially unsubstituted naphthyl or phenyl.
  • These alkyl radicals and also the cycloalkyl or aryl groups may be mono- or poly-substituted, for example by hydroxy, carboxy, halogen, cyano, amino or C1-C4alkoxy.
  • The alkoxy radicals may have from 1 to 12 carbon atoms, preferably from 1 to 4 carbon atoms and are, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy and n-hexyloxy. The alkoxy groups also may be substituted, for example by the radicals listed as possible substituents for the alkyl groups, especially by hydroxy or C1-C4alkoxy.
  • In the dyes of formula (1) and copper complexes thereof, Z2 is preferably hydrogen, hydroxy, alkoxy, amino, NH—COO—C1-C4alkyl, or anilino which is unsubstituted or substituted by amino and/or by sulfo.
  • Z1 is preferably NH—COO—C1-C4alkyl or the 4-amino-3-sulfo-anilino radical.
  • R2 and R4 are preferably hydrogen, C1-C4alkyl or C1-C4alkoxy.
  • In especially preferred dyes, Z1 and Z2 are identical and each is NH—COO—C1-C4alkyl or the 4-amino-3-sulfo-anilino radical.
  • The dyes of formula (1) are prepared in a manner known per se, for example a diamine of formula
    Figure US20060229440A1-20061012-C00006
    is tetraazotised in known manner and coupled with 2 moles of a coupling component of formula
    Figure US20060229440A1-20061012-C00007
    or with 1 mole each of a coupling component of formula (4) and a coupling component of formula
    Figure US20060229440A1-20061012-C00008
    under conditions known per se.
  • It is also possible first to prepare the monoazo compounds of formulae
    Figure US20060229440A1-20061012-C00009
    and to react 2 moles of a compound of formula (6) or 1 mole of a compound of formula (6) and 1 mole of a compound of formula (7) with a compound U—X—U′, QH and Q′H in each case being a group which can be replaced with a bridging member of formula X with removal of UH and U′H, respectively.
  • Such reactions have been described many times in the literature for the preparation of bridged disazo dyes.
  • When X is an azoxy group, the corresponding compounds of formula (1) can also be prepared in a manner likewise known per se by diazotisation of unsubstituted or substituted p-nitroanilines, coupling with a coupling component of formula (4) and/or (5) and subsequent reduction, for example using glucose.
  • The dyes of formula (1) which contain a free amino group can, in many cases, be prepared in pure form only with difficulty. An improvement can be achieved by introducing a protecting group which is subsequently removed. That is the case especially for those dyes wherein X is azoxy. Suitable protecting groups are those that are readily removable and that are stable under the conditions of the basic azoxy condensation. An alkoxycarbonyl group, especially the ethoxycarbonyl group, is especially suitable.
  • The mono- or bis-copper complexes of dyes of formula (2) are obtained in a manner known per se by means of copper-treatment of the customarily prepared dyes of formula (1) using copper-yielding agents in amounts of from 1 to 2.5 moles of copper per mole of dye of formula (1). The copper-treatment can also be carried out by demethylation as a result of cleavage of an alkoxy group or oxidatively with introduction of an additional oxygen group.
  • The invention preferably relates to the mono-copper complexes of dyes of formula (2) and mixtures thereof with the bis-copper complexes of such dyes.
  • These are obtained in a manner known per se by means of copper-treatment of the conventionally prepared dyes of formula (2) using copper-yielding agents in amounts of from 1 to 1.5 moles of copper per mole of dye of formula (2).
  • Depending upon the nature of the bridging member X, it is also possible for one of the halves of the dye of formula (2) that are connected by X to be reacted with up to 1 mole of copper-yielding agent and then to be connected to the second, non-copper-treated half by a direct bond or via the bridging member X. It is preferred, however, to start from the dye of formula (2) and to react that dye with a copper-yielding agent.
  • The dyes of formula (1) and the mono- and bis-copper complexes of dyes of formula (2) are suitable for dyeing natural and synthetic material.
  • The material is, for example, fibre material of leather, wool, polyamide, glass fibres or cotton and, especially, paper.
  • Using customary dyeing methods, blue dyeings having good fastness properties are obtained on such materials. Dyeings using the copper complexes especially have excellent light-fastness properties. The shade and the light-fastness can be controlled by the amount of copper used. When preparing mixtures of the mono-copper complexes with the bis-copper complexes, the amount of free copper in the effluents from synthesis can be reduced to a value of under 100 ppm whilst still obtaining good light-fastness properties.
  • The invention relates also to the use, for dyeing paper, of dyes of formula
    Figure US20060229440A1-20061012-C00010
    wherein
    • Z′1 is NHR6,
    • R6 being a radical of formula CO—R8, CO—NH—R8, SO2-alkyl, SO2-aryl,
      Figure US20060229440A1-20061012-C00011
    •  COOR8,
    • R8 being hydrogen, alkyl or aryl and
    • R7 being COOH or SO3H in the o-position to the NH2 group,
    • Z′2 is as defined for Z′1 or is hydrogen, hydroxy, alkoxy or a radical NHR5,
    • R5 being hydrogen, alkyl, aryl, COR8, CO—NHR8 or SO2R8,
    • R1 and R3 are each independently of the other hydrogen, hydroxy, alkyl or alkoxy,
    • R2 and R4 are each independently of the other hydrogen, hydroxy, alkyl or alkoxy, halogen, sulfo, carboxy, NHCONHR8 or NHCOR8,
    • X is a bridging member or a direct bond,
    • n and m are each independently of the other 1 or 2,
      and wherein the rings A and B may each independently of the other carry a fused-on benzene ring, it not being possible for both Z′1 and Z′2 simultaneously to be acetylamino or benzoylamino when X is a bridging member of formula —C═C—, and with the proviso that the compound of formula
      Figure US20060229440A1-20061012-C00012
      is excluded.
  • The dyes of formula (1) and the copper complexes of dyes of formula (2) or the mixtures of mono-copper complex with the bis-copper complex are preferably used as solid or liquid commercial forms.
  • In the form of powder or granules, the dyes are used especially in discontinuous mass dyeing, the dyes being added usually in the form of a stock solution to the pulper, hollander or mixing vat. In this case dye preparations are preferably used which may also comprise, besides the dye, diluents, e.g. urea as solubiliser, dextrin, Glauber's salt, sodium chloride and dispersants, dusting agents and sequestrants, such as tetrasodium phosphate.
  • The invention accordingly relates also to solid dye preparations for dyeing paper, which preparations comprise a dye of formula (1) according to the invention or a mono- or bis-copper complex of a dye of formula (2).
  • In recent years, the use of concentrated aqueous solutions of dyes has gained in importance, specifically because of the advantages which such solutions have over dyes in powder form. By using solutions, the difficulties associated with the formation of dust are avoided and the users are freed from the time-consuming and often difficult dissolution of the dye powder in water. The use of concentrated solutions has been prompted furthermore by the development of continuous dyeing processes for paper, since in those processes it is advantageous to add the solution in metered amounts directly to the pulp flow or at any other suitable point in the paper-making.
  • The invention accordingly relates also to concentrated aqueous solutions of the dyes of formula (1) used in accordance with the invention or of the mono- or bis-copper complexes of dyes of formula (2) for dyeing paper, which solutions contain from 5 to 30% by weight of dye, based on the total weight of the solution.
  • The concentrated solutions may comprise further auxiliaries, for example solubilisers, such as ε-caprolactam or urea, organic solvents, such as glycols, polyethylene glycols, dimethyl sulfoxide, N-methylpyrrolidone, acetamide, alkanolamines or polyglycolamines.
  • The following Examples serve to illustrate the invention but do not limit the invention thereto. Parts and percentages relate to weight, unless otherwise indicated.
    • EXAMPLE 1
  • 127.6 parts of 1-amino-8-naphthol-3,6-disulfonic acid are dissolved in 600 parts of water containing 30% sodium hydroxide solution at pH 6.5 to 7; the solution is then adjusted to a pH of 2.5 using 32% hydrochloric acid and stirred to form a homogeneous suspension. Starting at a temperature of 5° C., 54 parts of chloroformic acid ethyl ester are added dropwise over 1 hour, in the course of which the temperature rises to about 32° C., the pH being maintained at 2.5 by the dropwise addition of 30% sodium hydroxide solution. Heating at 35° C. is carried out until no more sodium hydroxide solution is used.
  • In a separate vessel, 16.8 parts of 2-amino-5-nitroanisole are diazotised in 100 parts of water containing 32% hydrochloric acid and sodium nitrite. The reaction solution is then coupled with 43 parts of the above-described 1-ethoxycarbonyl-8-naphthol-3,6-disulfonic acid in 170 parts of water at room temperature and pH 7 with addition of 30% sodium hydroxide solution. The suspension obtained is heated to a temperature of from 50 to 60° C.; 110 parts of 30% sodium hydroxide solution are added and, in the course of 1 hour, a solution of 15 parts of glucose in 60 parts of water is added. As soon as no more starting material is detectable, the pH is adjusted to 7.5 using 32% hydrochloric acid, with cooling, salted out with 60 parts of sodium chloride and filtered. The dye of formula
    Figure US20060229440A1-20061012-C00013
    is obtained. It dyes cellulose fibres, especially paper, brilliant reddish-blue shades having good fastness properties and with a high degree of exhaustion.
    • EXAMPLES 2-11
  • By proceeding as described in Example 1, but using the coupling components listed in the following Table, dyes are obtained that have similarly good properties, especially when dyeing paper.
    Example Coupling Component
    2 1-methoxycarbonylamino-8-naphthol-3,6-disulfonic acid
    3 1-ethoxycarbonylamino-8-naphthol-2,4-disulfonic acid
    4 1-ethoxycarbonylamino-8-naphthol-4,6-disulfonic acid
    5 2-ethoxycarbonylamino-5-naphthol-1,7-disulfonic acid
    6 3-ethoxycarbonylamino-5-naphthol-2,7-disulfonic acid
    7 2-ethoxycarbonylamino-5-naphthol-7-sulfonic acid
    8 3-ethoxycarbonylamino-5-naphthol-7-sulfonic acid
    9 2-ethoxycarbonylamino-5-naphthol-4,8-disulfonic acid
    10 2-(4-amino-3-sulfo-anilino)-5-naphthol-7-sulfonic acid
    11 3-(4-amino-3-sulfo-anilino)-5-naphthol-7-sulfonic acid
    • EXAMPLE 12
  • 28 parts of 4,4′-diamino-3,3′-dimethoxy-azobenzene are tetraazotised in 200 parts of water containing 40 parts of 32% hydrochloric acid and 50 ml of 4N sodium nitrite solution at 0-5° C. Then, at 10-20° C., coupling to 86 parts of 2-ethoxycarbonylamino-5-naphthol-1,7-disulfonic acid, dissolved in 250 parts of water, is carried out, the pH being maintained at 7.5-8 by the addition of 30% sodium hydroxide solution. Then, salting-out using 80 parts of sodium chloride and filtration are carried out. A dye is obtained that has similarly good properties to the dye described in Example 1.
    • EXAMPLES 13-62
  • By proceeding as described in Example 12, but using the diamines listed in the following Table together with 2 equivalents of the listed coupling components, dyes are obtained that have similarly good properties, especially when dyeing paper. It is also possible, in a manner known per se, first to react the first diazo group of the diamine with a first coupling component and then to react the second diazo group with a second coupling component.
    Example Diamine Coupling Component
    13 4,4′-diamino-3,3′-dimethoxy- 1-ethoxycarbonylamino-8-naphthol-3,6-
    azobenzene disulfonic acid
    14 4,4′-diamino-3,3′-dimethoxy- 1-methoxycarbonylamino-8-naphthol-
    azobenzene 3,6-disulfonic acid
    15 4,4′-diamino-3,3′-dimethoxy- 3-ethoxycarbonylamino-5-naphthol-2,7-
    azobenzene disulfonic acid
    16 4,4′-diamino-3,3′-dimethoxy- 2-ethoxycarbonylamino-5-naphthol-1,7-
    azobenzene disulfonic acid
    17 4,4′-diamino-3,3′-dimethoxy- 2-ethoxycarbonylamino-5-naphthol-4,8-
    azobenzene disulfonic acid
    18 4,4′-diamino-3,3′-dimethoxy- 2-(4-amino-3-sulfo-anilino)-5-naphthol-
    azobenzene 7-sulfonic acid
    19 4,4′-diamino-3,3′-dimethoxy- 1st coupling comp.: 2-ethoxycarbonylamino-
    azobenzene 5-naphthol-7-sulfonic acid
    2nd coupling comp.: 2-ethoxycarbonylamino-
    5-naphthol-1,7-disulfonic acid
    20 4,4′-diamino-azobenzene 1-ethoxycarbonylamino-8-naphthol-3,6-
    disulfonic acid
    21 4,4′-diamino-2′-methyl-azobenzene 1-ethoxycarbonylamino-8-naphthol-3,6-
    disulfonic acid
    22 4,4′-diamino-2′-methyl-azobenzene 3-ethoxycarbonylamino-5-naphthol-1,7-
    disulfonic acid
    23 4,4′-diamino-2′-methyl-azobenzene 1st coupling comp.: 1-naphthol-3,6-
    disulfonic acid
    2nd coupling comp.: 2-ethoxycarbonylamino-
    5-naphthol-7-disulfonic acid
    24 4,4′-diamino-2′-methyl-azobenzene 2-ethoxycarbonylamino-5-naphthol-4,8-
    disulfonic acid
    25 4,4′-diamino-2′-methyl-azobenzene 2-(4-amino-3-sulfo-anilino)-5-naphthol-
    7-sulfonic acid
    26 4,4′-diamino-2′,5′-dimethyl- 1-ethoxycarbonylamino-8-naphthol-3,6-
    azobenzene disulfonic acid
    27 4,4′-diamino-2′,5′-dimethyl- 2-ethoxycarbonylamino-5-naphthol-1,7-
    azobenzene disulfonic acid
    28 4,4′-diamino-3′-methoxy-azobenzene 1-ethoxycarbonylamino-8-naphthol-3,6-
    disulfonic acid
    29 4,4′-diamino-3′-methoxy-azobenzene 2-ethoxycarbonylamino-5-naphthol-1,7-
    disulfonic acid
    30 4,4′-diamino-2′-methoxy-azobenzene 1-ethoxycarbonylamino-8-naphthol-3,6-
    disulfonic acid
    31 4,4′-diamino-2′-methoxy-azobenzene 2-ethoxycarbonylamino-5-naphthol-1,7-
    disulfonic acid
    32 4,4′-diaminostilbene 1-ethoxycarbonylamino-8-naphthol-3,6-
    disulfonic acid
    33 4,4′-diaminostilbene 1-methoxycarbonylamino-8-naphthol-
    3,6-disulfonic acid
    34 4,4′-diaminostilbene 3-ethoxycarbonylamino-5-naphthol-2,7-
    disulfonic acid
    35 4,4′-diaminostilbene 2-ethoxycarbonylamino-5-naphthol-1,7-
    disulfonic acid
    36 4,4′-diaminostilbene 2-ethoxycarbonylamino-5-naphthol-4,8-
    disulfonic acid
    37 4,4′-diaminostilbene 2-(4-amino-3-sulfo-anilino)-5-naphthol-
    7-sulfonic acid
    38 4,4′-diamino-3,3′-dimethoxy-stilbene 1-ethoxycarbonylamino-8-naphthol-3,6-
    disulfonic acid
    39 4,4′-diamino-3,3′-dimethoxy-stilbene 2-ethoxycarbonylamino-5-naphthol-1,7-
    disulfonic acid
    40 4,4′-diamino-3-methoxy-stilbene 1-ethoxycarbonylamino-8-naphthol-3,6-
    disulfonic acid
    41 4,4′-diamino-3-methoxy-stilbene 2-ethoxycarbonylamino-5-naphthol-1,7-
    disulfonic acid
    42 4,4′-diaminostilbene-2,2′-disulfonic 2-ethoxycarbonylamino-5-naphthol-7-
    acid sulfonic acid
    43 4,4′-diaminostilbene-2,2′-disulfonic 1st coupling comp.: 3-ethoxycarbonylamino-
    acid 5-naphthol-7-sulfonic acid
    2nd coupling comp.: 1-amino-8-
    naphthol-3,6-disulfonic acid
    44 4,4′-diamino-diphenylamine 1-ethoxycarbonylamino-8-naphthol-3,6-
    disulfonic acid
    45 4,4′-diamino-diphenylamine 1-acetylamino-8-naphthol-3,6-disulfonic
    acid
    46 4,4′-diamino-diphenylamine 1-ureido-8-naphthol-3,6-disulfonic acid
    47 4,4′-diamino-diphenylamine 1-methylsulfonylamino-8-naphthol-3,6-
    disulfonic acid
    48 4,4′-diamino-diphenylamine 1-phenylsulfonylamino-8-naphthol-3,6-
    disulfonic acid
    49 4,4′-diamino-diphenylamine 1-p-tolylsulfonylamino-8-naphthol-3,6-
    disulfonic acid
    50 4,4′-diamino-2-sulfo-diphenylamine 1st coupling comp.: 3-ethoxycarbonylamino-
    2-naphthol-7-sulfonic acid
    2nd coupling comp.: 1-amino-8-
    naphthol-3,6-disulfonic acid
    51 4,4′-diamino-3,3′-dimethoxy- 1-ethoxycarbonylamino-8-naphthol-3,6-
    diphenylurea disulfonic acid
    52 4,4′-diamino-3,3′-dimethoxy- 1-acetylamino-8-naphthol-3,6-disulfonic
    diphenylurea acid
    53 4,4′-diamino-3,3′-dimethoxy- 1-ureido-8-naphthol-3,6-disulfonic acid
    diphenylurea
    54 4,4′-diamino-3,3′-dimethoxy- 1-methylsulfonylamino-8-naphthol-3,6-
    diphenylurea disulfonic acid
    55 4,4′-diamino-3,3′-dimethoxy- 1-phenylsulfonylamino-8-naphthol-3,6-
    diphenylurea disulfonic acid
    56 4,4′-diamino-3,3′,2,2′-tetramethoxy- 1-ethoxycarbonylamino-8-naphthol-3,6-
    diphenylurea disulfonic acid
    57 2,4-di(3′-methoxy-4′-amino-phenyl- 1-ethoxycarbonylamino-8-naphthol-3,6-
    amino)-6-di(2′-hydroxy-ethyl-amino)- disulfonic acid
    1,3,5-triazine
    58 2,4-di(3′-methoxy-4′-amino-phenyl- 1-acetylamino-8-naphthol-3,6-disulfonic
    amino)-6-di(2′-hydroxy-ethyl-amino)- acid
    1,3,5-triazine
    59 2,4-di(3′-methoxy-4′-amino-phenyl- 1-ureido-8-naphthol-3,6-disulfonic acid
    amino)-6-di(2′-hydroxy-ethyl-amino)-
    1,3,5-triazine
    60 2,4-di(3′-methoxy-4′-amino-phenyl- 1-methylsulfonylamino-8-naphthol-3,6-
    amino)-6-di(2′-hydroxy-ethyl-amino)- disulfonic acid
    1,3,5-triazine
    61 2,4-di(3′-methoxy-4′-amino-phenyl- 1-phenylsulfonylamino-8-naphthol-3,6-
    amino)-6-di(2′-hydroxy-ethyl-amino)- disulfonic acid
    1,3,5-triazine
    62 4,4′-diamino-3,3′-dimethoxy-biphenyl 1st coupling comp.: 1-ethoxycarbonylamino-
    8-naphthol-3,6-disulfonic acid
    2nd coupling comp.: 2-(4-amino-3-
    sulfoanilino)-5-naphthol-7-sulfonic acid
    • EXAMPLES 63-68
  • The dyes described in Examples 28, 29, 40 and 41 are converted, in a manner known per se, into the mono-copper complexes, by means of “demethylating copper-treatment”. These complexes are especially suitable for dyeing paper with good fastness properties.
    • EXAMPLES 69-102
  • The dyes described in Examples 1-19, 38, 39 and 51-62 are converted, in a manner known per se, into the bis-copper complexes, by means of “demethylating copper-treatment”. These complexes are especially suitable for dyeing paper with good fastness properties.
    • EXAMPLE 103
  • 100 parts of 50% sodium hydroxide solution are added to the crude synthesis solution of the dye described in Example 2 and stirring is carried out for 3 hours at a temperature of from 90 to 95° C. until hydrolysis is complete.
  • Neutralisation is then carried out using 32% hydrochloric acid and the precipitated dye is filtered off at room temperature. Without further purification operations, there is obtained, in a very high yield, a dye that dyes paper a considerably more brilliant shade than the corresponding dye synthesised without use of the protecting group.
  • The corresponding dyes having a free amino group can be obtained in analogous manner from the precursors described in Examples 3 to 10, 12, 13, 18, 19, 23, 25, 27, 29, 35, 37, 41, 44, 51, 56 and 57.

Claims (13)

1. A solid dye preparation for dyeing paper comprising a copper complex of formula
Figure US20060229440A1-20061012-C00014
wherein
Z1 is NHR6,
R6 being a radical of formula CO—R8, CO—NH—R8, SO2-alkyl, SO2-aryl,
Figure US20060229440A1-20061012-C00015
 COOR8,
R8 being hydrogen, alkyl or aryl and
R7 being COOH or SO3H in the o-position to the NH2 group,
Z2 is as defined for Z1 or is hydrogen, hydroxy, alkoxy or a radical NHR5,
R5 being hydrogen, alkyl, aryl, COR8, CO—NHR8 or SO2R8,
R1 and R3 are each independently of the other hydrogen, hydroxy, alkyl or alkoxy,
R2 and R4 are each independently of the other hydrogen, hydroxy, alkyl or alkoxy, halogen, sulfo, carboxy, NHCONHR8 or NHCOR8,
X is a direct bond in which case symmetrical compounds wherein Z1 and Z2 are NHCOCH3, NHCOOCH3 or NHCO-phenyl are excluded, or is —C═C— in which case both Z1 and Z2 cannot simultaneously be acetylamino, benzoylamino or 4-amino-3-sulfo-anilino, or is azo, azoxy, —NR8, —NR8CONR9— or a group of formula
Figure US20060229440A1-20061012-C00016
Y being hydroxy, alkoxy or NR9R10,
R9 and R10 being each independently of the other hydrogen, unsubstituted or substituted alkyl or unsubstituted or substituted aryl,
n and m are each independently of the other 1 or 2,
and wherein the rings A and B may each independently of the other carry a fused-on benzene ring,
with the proviso that the compounds of formulae
Figure US20060229440A1-20061012-C00017
are excluded and optionally, further additives.
2. A mono- or bis-copper complex of a dye of formula
Figure US20060229440A1-20061012-C00018
wherein
R1 and/or R3 are hydroxy or alkoxy,
Z1 is NHR6,
R6 being a radical of formula CO—R8, CO—NH—R8, SO2-alkyl, SO2-aryl,
Figure US20060229440A1-20061012-C00019
 COOR8,
R8 being hydrogen, alkyl or aryl and
R7 being COOH or SO3H in the o-position to the NH2 group,
Z2 is as defined for Z1 or is hydrogen, hydroxy, alkoxy or a radical NHR5,
R5 being hydrogen, alkyl, aryl, COR8, CO—NHR8 or SO2R8,
R2 and R4 are each independently of the other hydrogen, hydroxy, alkyl or alkoxy, halogen, sulfo, carboxy, NHCONHR8 or NHCOR8,
X is a direct bond in which case symmetrical compounds wherein Z1 and Z2 are NHCOCH3, NHCOOCH3 or NHCO-phenyl are excluded, or is —C═C— in which case both Z1 and Z2 cannot simultaneously be acetylamino, benzoylamino or 4-amino-3-sulfo-anilino, or is azo, azoxy, —NR8, —NR8CONR9— or a group of formula
Figure US20060229440A1-20061012-C00020
Y being hydroxy, alkoxy or NR9R10,
R9 and R10 being each independently of the other hydrogen, unsubstituted or substituted alkyl or unsubstituted or substituted aryl,
n and m are each independently of the other 1 or 2,
and wherein the rings A and B may each independently of the other carry a fused-on benzene ring.
3. A dye according to claim 2, wherein Z2 is hydrogen, hydroxy, alkoxy, amino, NH—COO—C1-C4alkyl, or anilino which is unsubstituted or substituted by amino and/or by sulfo.
4. A dye according to 2, wherein Z1 is NH—COO—C1-C4alkyl or the 4-amino-3-sulfo-aniline radical.
5. A dye according to 2, wherein Z1 and Z2 are identical and each is NH—COO—C1-C4alkyl or the 4-amino-3-sulfo-aniline radical.
6. A dye according to claim 2, wherein R2 and R4 are each hydrogen, C1-C4alkyl or C1-C4alkoxy.
7. A mono-copper complex of a dye of formula
Figure US20060229440A1-20061012-C00021
wherein
R1 and/or R3 are hydroxy or alkoxy,
Z1 is NHR6,
R6 being a radical of formula CO—R8, CO—NH—R8, SO2-alkyl, SO2-aryl,
Figure US20060229440A1-20061012-C00022
 COOR8,
R8 being hydrogen, alkyl or aryl and
R7 being COOH or SO3H in the o-position to the NH2 group,
Z2 is as defined for Z1 or is hydrogen, hydroxy, alkoxy or a radical NHR5, R5 being hydrogen, alkyl, aryl, COR8, CO—NHR8 or SO2R8,
R1 and R3 are each independently of the other hydrogen, hydroxy, alkyl or alkoxy,
R2 and R4 are each independently of the other hydrogen, hydroxy, alkyl or alkoxy, halogen, sulfo, carboxy, NHCONHR8 or NHCOR8,
X is a direct bond in which case symmetrical compounds wherein Z1 and Z2 are NHCOCH3, NHCOOCH3 or NHCO-phenyl are excluded, or is —C═C— in which case both Z1 and Z2 cannot simultaneously be acetylamino, benzoylamino or 4-amino-3-sulfo-anilino, or is azo, azoxy, —NR8, —NR8CONR9— or a group of formula
Figure US20060229440A1-20061012-C00023
Y being hydroxy, alkoxy or NR9R10,
R9 and R10 being each independently of the other hydrogen, unsubstituted or substituted alkyl or unsubstituted or substituted aryl,
n and m are each independently of the other 1 or 2,
and wherein the rings A and B may each independently of the other carry a fused-on benzene ring,
and
a mixture thereof with a bis-copper complex of a dye of formula (I)
Figure US20060229440A1-20061012-C00024
wherein the substituents are defined as above and optionally, further additives.
8. A concentrated aqueous solution for dyeing paper, comprising a copper complex of a dye of formula (1)
Figure US20060229440A1-20061012-C00025
wherein
Z1 is NHR6,
R6 being a radical of formula CO—R8, CO—NH—R8, SO2-alkyl, SO2-aryl,
Figure US20060229440A1-20061012-C00026
 COOR8,
R8 being hydrogen, alkyl or aryl and
R7 being COOH or SO3H in the o-position to the NH2 group,
Z2 is as defined for Z1 or is hydrogen, hydroxy, alkoxy or a radical NHR5,
R5 being hydrogen, alkyl, aryl, COR8, CO—NHR8 or SO2R8,
R1 and R3 are each independently of the other hydrogen, hydroxy, alkyl or alkoxy,
R2 and R4 are each independently of the other hydrogen, hydroxy, alkyl or alkoxy, halogen, sulfo, carboxy, NHCONHR8 or NHCOR8,
X is a direct bond in which case symmetrical compounds wherein Z1 and Z2 are NHCOCH3, NHCOOCH3 or NHCO-phenyl are excluded, or is —C═C— in which case both Z1 and Z2 cannot simultaneously be acetylamino, benzoylamino or 4-amino-3-sulfo-anilino, or is azo, azoxy, —NR8, —NR8CONR9— or a group of formula
Figure US20060229440A1-20061012-C00027
Y being hydroxy, alkoxy or NR9R10,
R9 and R10 being each independently of the other hydrogen, unsubstituted or substituted alkyl or unsubstituted or substituted aryl,
n and m are each independently of the other 1 or 2,
and wherein the rings A and B may each independently of the other carry a fused-on benzene ring,
with the proviso that the compounds of formulae
Figure US20060229440A1-20061012-C00028
are excluded and optionally, further additives.
9. Paper dyed using a solid dye of formula (1) according to claim 1.
10. Paper dyed using a concentrated aqueous solution for dyeing paper according to claim 8.
11. A concentrated aqueous solution for dyeing paper, comprising a dye according to claim 2 and optionally, further additives.
12. A solid dye preparation for dyeing paper, comprising a dye according to claim 2 and optionally, further additives.
13. Paper dyed using a dye according to claim 2.
US11/446,848 2000-12-28 2006-06-05 Disazo dyes, and copper complexes thereof, for dyeing paper Abandoned US20060229440A1 (en)

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KR20030064892A (en) 2003-08-02
EP1345992B1 (en) 2006-07-05
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EP1345992A2 (en) 2003-09-24
US20040063920A1 (en) 2004-04-01
US7078497B2 (en) 2006-07-18
AU2002238450B2 (en) 2006-08-17
ES2269490T3 (en) 2007-04-01
CN1483063A (en) 2004-03-17
BR0116593A (en) 2003-12-23
ATE332337T1 (en) 2006-07-15
CA2431043A1 (en) 2002-07-11
WO2002053649A2 (en) 2002-07-11
DE60121363T2 (en) 2007-06-28
JP2004517189A (en) 2004-06-10
WO2002053649A3 (en) 2003-03-06

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