EP1877495A2 - Colorants reactifs azo, leurs procedes de production, et leur utilisation - Google Patents

Colorants reactifs azo, leurs procedes de production, et leur utilisation

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Publication number
EP1877495A2
EP1877495A2 EP06806725A EP06806725A EP1877495A2 EP 1877495 A2 EP1877495 A2 EP 1877495A2 EP 06806725 A EP06806725 A EP 06806725A EP 06806725 A EP06806725 A EP 06806725A EP 1877495 A2 EP1877495 A2 EP 1877495A2
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EP
European Patent Office
Prior art keywords
alkyl
substituted
hydrogen
general formula
interrupted
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.)
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Application number
EP06806725A
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German (de)
English (en)
Inventor
Gunter GÖRLITZ
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 Textilfarben GmbH and Co Deutschland KG
Original Assignee
Dystar Textilfarben GmbH and Co Deutschland KG
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Publication of EP1877495A2 publication Critical patent/EP1877495A2/fr
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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
    • C09B67/0051—Mixtures of two or more azo dyes mixture of two or more monoazo dyes
    • C09B67/0052—Mixtures of two or more reactive monoazo dyes
    • C09B67/0054—Mixtures of two or more reactive monoazo dyes all the reactive groups not being directly attached to a heterocyclic system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C07D213/85—Nitriles in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C09B62/4401—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 with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4403—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 with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
    • C09B62/4411—Azo dyes
    • C09B62/4413—Non-metallized monoazo 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
    • C09B62/4401—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 with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4403—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 with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
    • C09B62/4411—Azo dyes
    • C09B62/4415—Disazo or polyazo 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
    • C09B62/503—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 an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/51—Monoazo 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
    • C09B62/503—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 an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/513—Disazo or polyazo 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
    • 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
    • C09B67/0047—Mixtures of two or more reactive azo dyes
    • C09B67/005—Mixtures of two or more reactive azo dyes all the reactive groups being not directly attached to a heterocyclic system
    • 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
    • C09B67/0057—Mixtures of two or more reactive disazo dyes
    • C09B67/0059—Mixtures of two or more reactive disazo dyes all the reactive groups are not directly attached to a heterocyclic system

Definitions

  • Reactive azo dyes process for their preparation and their use
  • the present invention is in the field of fiber-reactive dyes. From the documents DE 3 025 904, EP 0 581 730 and EP 0 581 731 dyes are already known which have structural similarities with the dyes according to the invention described below, but differ with respect to the reactive anchor in the coupling component. These known dyes have a number of technical disadvantages in the dyeing of textile materials, which was to be improved.
  • the present invention relates to reactive dyes of the general formula (1),
  • D is the radical of a diazo component of the benzene or naphthalene series, a heterocyclic radical or the radical of a mono- or disazo dye,
  • R 1 is C 1 -C 4 -alkyl
  • R 2 is cyano, carbamoyl or sulfomethyl
  • R 3, R 4 and R 5 are independently hydrogen or optionally substituted by hydroxy, sulfo, sulfato or vinylsulfonyl substituted and with the exception of methyl, may be interrupted by oxygen or NR 7 C r C 18 alkyl or C 4 - C 7 cycloalkyl, wherein R 7 is hydrogen or C r C 4 alkyl or R 3 and R 4 are part of heterocyclic groups,
  • Q is C r C 18 -alkylene which is optionally substituted by C 1 -C 4 -alkyl, halogen or hydroxyl and is interrupted, with the exception of methylene, optionally by oxygen or NR 7 , n is 0 or 1,
  • Ar is an unsubstituted or substituted by sulfo, carboxy, C r C 4 alkyl, C r C 4 alkoxy or halogen-substituted phenylene or naphthylene radical,
  • D preferably represents a group of the general formula (DI) (D-II) or (D-XII),
  • R D1 and R D2 are independently hydrogen, (C r C4) alkyl, ( C r C 4 ) -alkoxy,
  • X m has one of the meanings of R m or R D 2 or for a group of
  • Z has one of the meanings of Y or D represents a naphthyl group of the general formula (D-III),
  • R D3 and R D4 are independently hydrogen, (C r C4) alkyl, (C r C 4) -alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, Amido, ureido or halogen; and X D2 has one of the meanings of X m ; or
  • D is a group of general formula (D-IV),
  • M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaline earth metal or organic monovalent cations, in particular alkylammonium, R D5 and R D6 independently one of the meanings of R m and Have R D2 ;
  • R D7 is hydrogen, (C 1 - C 4) alkyl, unsubstituted or substituted by (C 1 -C 4) - alkyl, (C r C4) -alkoxy, sulfo, halogen or carboxy substituted phenyl; and Z D2 is a group of general formula (DV) or (D-VI) or (D-VII), wherein
  • V is fluorine or chlorine
  • U m , U D2 are independently fluorine, chlorine or hydrogen; and Q m , Q D2 independently of one another chlorine, fluorine, cyanamido, hydroxy, (C 1 -
  • R D8 is hydrogen or (C r C 6) alkyl, sulfo (C r C6) alkyl, or phenyl which is unsubstituted or substituted by (C r C4) alkyl, (C 1 - C4) alkoxy, Sulfo, halogen, carboxy, acetamido, ureido is substituted;
  • R D9 and R mo independently of one another have one of the meanings of R D8 , or form a cyclic ring system of the formula - (CH 2 ) -, where j is 4 or 5, or alternatively - (CH 2 ) 2 -E- (CH 2 ) 2 -, wherein E is oxygen, sulfur, sulfo, -NR D11 and R mi (C r C 6 ) alkyl; W is phenylene which is unsubstituted or substituted by 1 or 2
  • Substituents such as (C r C 4 ) alkyl, (C r C 4 ) alkoxy, carboxy, sulfo, chlorine, bromine, or W is (C r C 4 ) -alkylene-arylene or (C 2 -C 6 ) -alkylene, which may be interrupted by oxygen, sulfur, sulfo, amino, carbonyl,
  • W is phenylene-CONH-phenylene which is unsubstituted or substituted by (C 1 -C 4) - alkyl, (C r C 4) -alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido or
  • Halogen is substituted or W is naphthylene which is unsubstituted or substituted by one or two
  • D is a group of general formula (D-X) or (D-Xl),
  • R D12 has one of the meanings of R m
  • X D3 has one of the meanings of X m has X D4 -CN and COOR 013
  • R 13 has one of the meanings of R and R is C 1 -C 4 alkyl.
  • Alkali eliminable substituents Y 1 which are in the ⁇ -position of the ethyl group of Y are, for example, halogen atoms, such as chlorine and bromine, ester groups of organic carboxylic and sulfonic acids, such as alkylcarboxylic acids, optionally substituted benzenecarboxylic acids and optionally substituted benzenesulphonic acids, such as the alkanoyloxy groups of 2 to 5 C atoms, thereof in particular acetyloxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and toluenesulfonyloxy, further acidic Ester groups of inorganic acids, such as phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfato groups), as well as dialkylamino groups with alkyl groups of 1 to 4 carbon atoms, such as dimethylamino
  • Y is preferably ⁇ -sulfatoethyl, ⁇ -chloroethyl and particularly preferably vinyl.
  • sulfo groups means groups corresponding to the general formula -SO 3 M, thiosulfato groups corresponding to the general groups Formula -S-SO 3 M, carboxy groups groups corresponding to the general formula -COOM, phosphato groups corresponding to the general formula -OPO 3 M 2 and sulfato groups corresponding to the general formula -OSO 3 M, wherein M is hydrogen, an alkali metal, ammonium, a Equivalent to an alkaline earth metal or organic monovalent cations, in particular alkylammonium means.
  • Preferred reactive dyes according to the invention are those of the general formula (1 a)
  • Very particularly preferred reactive dyes according to the invention are those of the general formula (1 d),
  • X xD1 has one of the meanings of R or R and R and R, Ar, Q and Y are as defined above and R 5 is hydrogen or C r C 1 ⁇ alkyl.
  • R 2 is cyano, carbamoyl or sulfomethyl
  • R 3 and R 4 are independently hydrogen or optionally substituted by hydroxy, sulfo, sulfato, or vinylsulfonyl-substituted and with
  • methyl may be interrupted by oxygen or NR 7 C r C 18 alkyl or C 4 - C 7 cycloalkyl mean wherein R 7 is hydrogen or C r C 4 alkyl, or R 3 and R 4 are part of heterocyclic groups, R 5 are hydrogen or C r C 18 alkyl, Q is C r C 18 -alkylene which is unsubstituted or substituted by C 1 -C 4 -alkyl, halogen or hydroxyl and is optionally interrupted by oxygen or NR 7 , with the exception of methylene, and
  • R 1 is C r C 4 alkyl
  • R 2 is cyano, carbamoyl or sulfomethyl
  • R 3 and R 4 are independently hydrogen or optionally
  • C 7 cycloalkyl wherein R 7 is hydrogen or C r C 4 - hydroxy, sulfo, sulfato, or vinylsulfonyl substituted and 7 broken, with the exception of methyl, may be interrupted by oxygen or NR C r C 18 alkyl or C 4 - Is alkyl, or R 3 and R 4 are heterocyclic groups, R 5 is hydrogen or C r C 1 ⁇ alkyl, Q is optionally substituted by C 1 - C 4 _alkyl, halogen or hydroxy and, with the exception of methylene, optionally substituted by oxygen or NR 7 is interrupted C r C 18 -alkylene and (D-XII) and Y have the meanings given above.
  • the coupling component of the general formula (2) in the dyes of the invention are novel and also the subject of the invention.
  • the present invention accordingly furthermore relates to diaminopyridines of the general formula (2),
  • R 1 is C 1 -C 4 -alkyl 1
  • R 2 is cyano, carbamoyl or sulfomethyl
  • R 3 , R 4 and R 5 are independently hydrogen or optionally substituted by hydroxy, sulfo, sulfato, or vinylsulfonyl-substituted and with
  • methyl may be interrupted by oxygen or NR 7 C r C 18 alkyl or C 4 - C 7 cycloalkyl mean wherein R 7 is hydrogen or C r C 4 alkyl, or R 3 and R 4 are part of heterocyclic groups, Q is optionally substituted by C 1 - C 4 substituted _Alkyl, halogen or hydroxy and with the exception of methylene optionally interrupted by oxygen or NR 7 interrupted C r C 18 alkylene, n is 0 or 1,
  • Ar is an unsubstituted or substituted by sulfo, carboxy, C r C 4 alkyl, C 1 -C 4 -alkoxy or halogen-substituted phenylene or naphthylene radical
  • Y is -CH-CH 2 or -CH 2 CH 2 Y 1 , in which Y 1 is hydroxy or an alkali cleavable group.
  • Preferred diaminopyridines of the general formula (2) are, for example, the abovementioned diaminopyridines which may be present as an isomer mixture.
  • a compound of the general formula (2) or the formulas P (1) to P (25) contains an acid group, such as a group SO 3 H, this may also be in the form of a salt, for. B. with the group SO 3 M, where M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaline earth metal or organic monovalent cations, in particular alkylammonium means.
  • the present invention furthermore relates to processes for preparing the diaminopyridines of the general formula (2).
  • R 1 and R 2 are as defined above, reacted with one molar equivalent of an amine of the general formula (4), wherein
  • R 3 and R 4 are independently hydrogen or optionally
  • C 4 - C 7 are cycloalkyl, wherein R 7 is hydrogen or C r C 4 alkyl, or R 3 and
  • R 4 component of heterocyclic groups wherein the monoaminopyridine of the general formula (5) is obtained as a mixture of isomers.
  • R 1 is C r C 4 alkyl
  • R 2 is cyano, carbamoyl or sulfomethyl
  • R 5 is hydrogen or optionally substituted by hydroxy-substituted and with the exception of methyl optionally interrupted by oxygen or NR 7 C r C 18 alkyl or C 4 - 7 cycloalkyl
  • R 7 is hydrogen or C r C 4 alkyl
  • Q is C r C 18 -alkylene which is unsubstituted or substituted by C 1 -C 4 -alkyl, halogen or hydroxyl and is optionally interrupted by oxygen or NR 7
  • n is 0 or 1
  • Ar is an unsubstituted or by sulfo, carboxy, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or halogen-substituted phenylene or naphthylene radical
  • Y means -CH 2 CH 2 OH
  • Y is -CH 2 CH 2 OH
  • R 5 is hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl optionally interrupted by oxygen or NR 7 interrupted C r C 18 alkyl or C 4 - C 7 cycloalkyl, wherein R 7 is hydrogen or C r C 4 Alkyl,
  • Q is optionally substituted by C 1 - C 4 _Alkyl, halogen or hydroxy and, with the exception of methylene, optionally substituted by oxygen or
  • NR 7 is interrupted C r C 18 -alkylene, n is 0 or 1
  • Ar is an unsubstituted or substituted by sulfo, carboxy, C 1 -C 4 -AlkVl, C r C 4 alkoxy or halogen-substituted phenylene or naphthylene radical and
  • Y is -CH 2 CH 2 Y 1 , in which
  • Y 1 is hydroxy to form the corresponding monochloropyridine derivative of the general
  • R 1 is C r C 4 alkyl
  • R 2 is cyano, carbamoyl or sulfomethyl
  • R 5 is hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl, may be interrupted by oxygen or NR 7 C r C 18 alkyl or C 4 - C 7 cycloalkyl mean wherein R 7
  • NR 7 is interrupted C r C 18 -alkylene, n is 0 or 1,
  • Ar is an unsubstituted or substituted by sulfo, carboxy, C r C 4 alkyl, C r C 4 alkoxy or halogen-substituted phenylene or naphthylene radical and
  • Y is -CH 2 CH 2 Y 1 , in which
  • Y 1 is hydroxy, followed by oxidation to form the monochloropyridine of general formula (6).
  • R 2 is cyano, carbamoyl or sulfomethyl
  • R 3 and R 4 independently of one another denote hydrogen or C r C 18 -alkyl which is optionally interrupted by hydroxyl or sulfo, substituted and, with the exception of methyl, optionally interrupted by oxygen, sulfone or sulfonyl (-SO 2 -), or NR 7 4 - C 7 denote cycloalkyl, in which R 7
  • R 5 is hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl, may be interrupted by oxygen or NR 7 C r C 18 Alkyl or C 4 -C 7 cycloalkyl, in which R 7
  • Q is C r C 18 -alkylene which is optionally substituted by C 1 -C 4 -alkyl, halogen or hydroxyl and is interrupted, with the exception of methylene, optionally by oxygen or NR 7 , n is 0 or 1,
  • Ar is an unsubstituted or substituted by sulfo, carboxy, C r C 4 alkyl, C 1 -C 4 -alkoxy or halogen-substituted phenylene or naphthylene radical
  • Y is -CH 2 CH 2 Y 1 , in which
  • Y 1 is hydroxy, or d) by reacting the monochloropyridine of the general formula (9) with an amine of the general formula (4) and subsequent oxidation of the resulting intermediate of the formula (10), a diaminopyridine of the formula (2) is obtained which is obtained as a mixture of isomers, wherein the ratio of the isomers of the trodden synthesis route depends.
  • the oxidation is preferably carried out in water, an organic solvent or in a mixture of water and organic solvent.
  • Preferred organic solvents are, for example, acetic acid, dichloromethane or N-methylpyrrolidone.
  • Preferred temperatures for said oxidation are temperatures of 10 to 80 0 C, in particular from 30 to 50 0 C.
  • the said oxidation is advantageously carried out in the presence of a catalyst.
  • catalysts are salts which contain titanium, vanadium, manganese, molybdenum or tungsten or clays or clay mineral earths.
  • Particularly advantageous catalysts are, for. As sodium tungstate, montmorillonite or kaolin.
  • Suitable oxidizing agents are, for example, halogens or peroxides, such as. For example, chlorine, hydrogen peroxide, peroxodisulfates or peracids, such as. Eg
  • Chloroperbenzoic acid, peracetic acid or periodic acid or salts thereof, such as Oxone® in strongly acidic medium, said oxidation step may also be carried out with e.g. Sulfur trioxide or oleum are carried out in the presence of iodine-containing catalysts.
  • Another example of the oxidation step is the reaction with a halogen, e.g. B. with chlorine, the z. B. can be done in hydrochloric acid medium.
  • the preparation of the monoaminopyridines (5), (6) and (9) and the diaminopyridines (2) and (10) is usually carried out in water, an organic solvent such as toluene, butanol or N-methylpyrrolidone or without the use of a solvent temperatures of 30 to 150 0 C, preferably at 40 to 80 0 C, in the presence of a base, for example alkali metal carbonate, Alkali hydrogen carbonate, alkaline earth oxide, alkaline earth metal hydroxide, alkaline earth carbonate, or trialkylamine, preferably triethylamine or tributylamine.
  • a base for example alkali metal carbonate, Alkali hydrogen carbonate, alkaline earth oxide, alkaline earth metal hydroxide, alkaline earth carbonate, or trialkylamine, preferably triethylamine or tributylamine.
  • the desired secondary product can be prepared by reaction with the corresponding acid derivative or the corresponding acid, which can be converted in a conventional manner into the corresponding vinyl compound.
  • R 1 is C r C 4 alkyl
  • R 2 is cyano, carbamoyl or sulfomethyl
  • R 3 and R 4 independently of one another denote hydrogen or C r C 18 -alkyl which is optionally interrupted by hydroxyl or sulfo, substituted and, with the exception of methyl, optionally interrupted by oxygen, sulfone or sulfonyl (-SO 2 -), or NR 7 4 - C 7 cycloalkyl, wherein R 7 is hydrogen or C r C 4 alkyl, or R 3 and R 4 are part of heterocyclic
  • R 5 is hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl, may be interrupted by oxygen or NR 7 C r C 18 alkyl or C 4 - C 7 cycloalkyl mean wherein R 7 is hydrogen or C r C 4 - Alkyl is,
  • Q is C r C 18 -alkylene which is unsubstituted or substituted by C 1 -C 4 -alkyl, halogen or hydroxyl and is optionally interrupted by oxygen or NR 7 , n is 0 or 1, Ar is an unsubstituted or by sulfo, carboxy, C r C 4 alkyl, C r C 4 alkoxy or halogen-substituted phenylene or naphthylene radical, Y is -CH 2 CH 2 Y 1 in which
  • Y 1 denotes hydroxy with an acid derivative or an acid to give compounds of the formula (2) or to compounds of the formula (10) in which
  • R 1 is C r C 4 alkyl
  • R 2 is cyano, carbamoyl or sulfomethyl
  • R 3 and R 4 are independently hydrogen or optionally
  • R 5 is hydrogen or optionally substituted by hydroxy, sulfato, sulfo, substituted and with the exception of methyl optionally interrupted by oxygen or NR 7 C r C 18 alkyl or C 4 - C 7 cycloalkyl, wherein R 7 is hydrogen or C r C 4 alkyl is
  • Q is C r C 18 -alkylene which is unsubstituted or substituted by C 1 -C 4 -alkyl, halogen or hydroxyl and is optionally interrupted by oxygen or NR 7 , n is 0 or 1, Ar is an unsubstituted or by sulfo, carboxy, C 1 -C 4 -AlkVl, C r C 4 alkoxy or halogen substituted phenylene or naphthylene radical, Y is -CH 2 CH 2 Y 1 , wherein
  • Y 1 is a group which can be split off under the action of alkali, is preferably carried out in an organic solvent or without the use of solvents in the corresponding acid or the corresponding acid derivative.
  • Preferred acids or acid derivatives are, for example, acetic anhydride, sulfuric acid, oleum or sulfur trioxide monohydrate.
  • Preferred temperatures for said reaction are temperatures of -5 to 140 ° C, in particular from 5 to 40 0 C.
  • the said reaction with organic acid derivatives proceeds advantageously in the presence of a catalyst or dehydrating agent, wherein as catalysts pyridine or pyridine derivatives such.
  • a catalyst or dehydrating agent wherein as catalysts pyridine or pyridine derivatives such.
  • 4-diaminopyridine, 4-pyrrolidinopyridine, nicotinic acid, or pyridonaphthyridine are particularly preferred.
  • the compound of the general formula (10) can be derivatized with an acid or an acid derivative first and then oxidized, wherein an oxidation can already take place during the derivatization with an acid or an acid derivative.
  • an oxidation can already take place during the derivatization with an acid or an acid derivative.
  • substituents of R 1 to R 5 or of the groups Q or Ar it is also possible to derivatize substituents of R 1 to R 5 or of the groups Q or Ar.
  • substituents of R 1 to R 5 or of the groups Q or Ar can be derivatized at the groups mentioned z.
  • esterification saponification or oxidation take place, for. B.
  • hydroxy groups in R 3 to R 5 can also be esterified, as is also the case in the examples described below.
  • groups of R 1 to R 5 or groups of Q or Ar or their substituents can be derivatized in the described oxidations.
  • the synthesis of the bis-reactive diaminopyridines of the general formula (2) is also carried out by stepwise introduction of the amino substituents by reacting a dichloropyridine of the general formula (3) with compounds of the general formula (8), wherein Y 1 is hydroxy, followed by those described above Oxidation steps and optionally followed by the derivatization steps described above or by reacting a
  • the dyes according to the invention can be obtained by reacting the corresponding diazonium salts with a coupling component of the general formula (2) or (10), optionally followed by the oxidation and derivatization steps described above for the coupling component analogously for the dye synthesis.
  • the diazonium salts are prepared in the usual way by diazotization of the corresponding amines D-NH 2 .
  • Preferred amines for diazotization are shown in Table 1
  • the dyes of the general formula (1) according to the invention are obtained in the above-described preparation process as a solution or suspension and can be isolated by salting out. They can also be spray-dried, and evaporation of the solution or suspension is also possible.
  • reactive dyestuffs of the general formula (1) according to the invention are present as isomer mixtures, unless the isomers were separated at one stage of the synthesis of the dyestuff or diaminopyridine or an isomerically pure coupler was used for the synthesis of the dyestuff.
  • the reactive dyes of the general formula (1) according to the invention are generally present as a preparation in solid or in liquid form.
  • solid form they generally contain the water-soluble and in particular fiber-reactive Dyes conventional electrolyte salts, such as sodium chloride, potassium chloride and sodium sulfate, and may further contain the usual in commercial dyes aids, such as buffer substances that can adjust a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate , Sodium tricitrate and disodium hydrogen phosphate, small amounts of siccatives or, if present in liquid form (including the level of thickening agents common in printing pastes), substances which ensure the shelf life of these preparations, such as mildewproofing agents.
  • buffer substances that can adjust a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate , Sodium tricitrate and disodium hydrogen phosphate
  • the reactive dyes of the general formula (1) according to the invention as a dye powder or dye granules with a content of 10 to 80 wt .-%, based on the powder or the granules, of an electrolyte salt, which is also referred to as an adjusting agent before.
  • Granules have in particular grain sizes of 50 to 500 microns.
  • These solid preparations may also contain the mentioned buffer substances in a total amount of up to 10 wt .-%, based on the preparation. If the dyes are present in liquid preparation, the total dye content in these aqueous solutions is up to about 50% by weight, for example between 5 and 50% by weight.
  • the electrolyte salt content in these aqueous solutions is preferably below 10% by weight. , based on the aqueous solution.
  • the liquid preparations may contain the mentioned buffer substances usually in an amount of up to 10% by weight, preferably up to 2% by weight.
  • the reactive dyes of the general formula (1) according to the invention have valuable performance properties. They are used for dyeing and printing carbonamide and / or hydroxyl or amino-containing materials, for example in the form of fabrics, such as paper and leather or films, such as polyamide or in the mass, such as polyamide and polyurethane, but especially used in the form of fibers of the materials mentioned. They are used for dyeing and printing cellulosic fiber materials of all kinds. They are also preferably suitable for dyeing or printing polyamide fibers or blended fabrics Polyamide with cotton or with polyester fibers. It is also possible to use them to print textiles or paper using the inkjet process.
  • the present invention thus also relates to the use of the inventive reactive dyes of the general formula (1) for dyeing or printing said materials or processes for dyeing or printing such materials in per se conventional procedures, in which one or more inventive Reactive dyes of the general formula (1) used as a colorant.
  • the solutions of the reactive dyes of the general formula (1) according to the invention optionally after addition of a buffer substance, optionally also after concentration or dilution, can be fed directly as liquid preparation to the dyeing use.
  • the materials mentioned are preferably used in the form of fiber materials, in particular in the form of textile fibers, such as fabrics or yarns, such as in the form of strands or wound bodies.
  • Carboxamido-containing materials are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hair, silk, leather, polyamide-6,6, polyamide-6, polyamide-1 and polyamide-4.
  • Hydroxy-containing materials are those of natural or synthetic origin such as cellulosic fiber materials or their regenerated products and polyvinyl alcohols.
  • Cellulose fiber materials are preferably cotton, but also other vegetable fibers such as linen, hemp, jute and ramie fibers.
  • Regenerated cellulose fibers are, for example, rayon and viscose rayon.
  • novel reactive dyes of the general formula (1) can be on the substrates mentioned, in particular on the fiber materials mentioned, apply and fix according to the application techniques known for water-soluble, in particular according to the application techniques known for fiber-reactive dyes.
  • Felt-free or low-felt wool (compare, for example, H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd edition (1972), pp. 295-299, especially the equipment according to the so-called Hercosett method (p Soc. Dyers and Colorists 1972, 93-99, and 1975, 33-44) with very good fastness properties.
  • the process of dyeing wool is carried out here in the usual and well-known Därbeweise from an acidic environment.
  • acetic acid and / or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dyebath to obtain the desired pH.
  • conventional leveling agents such as those based on a reaction product of cyanuric chloride with three times the molar amount of a
  • the dye mixture according to the invention is preferably first subjected to the exhaustion process from acid dyebath having a pH of about 3.5 to 5.5 under the control of the pH, and the pH then, towards the end of the dyeing time, into the neutral and optionally weak shifted alkaline range to a pH of 8.5, especially to achieve high color depths, the full reactive binding between the dyes of the dye mixtures of the invention and the fiber bring about. At the same time, the non-reactively bound dye fraction is removed.
  • the procedure described here also applies to the production of dyeings on fiber materials from other natural polyamides or from synthetic polyamides and polyurethanes.
  • dyeing these materials, it is possible to use the customary dyeing and printing processes described in the literature and known to the person skilled in the art (see, for example, H. -K. Rouette, Handbuch der Textilveredlung, Deutscher ausverlag GmbH, Frankfurt am Main).
  • the dyeing liquors and printing pastes may contain other additives in addition to the dyes of the general formulas (I) and water.
  • Additives are for example Wetting agents, anti-foaming agents, leveling agents and the properties of the textile material influencing agents, such as softening agents, additives for flameproofing and dirt, water and oil repellent or water-softening agents.
  • printing pastes may also contain natural or synthetic thickeners, such as alginates and cellulose ethers.
  • the amounts of dye can vary within wide limits depending on the desired color depth.
  • the dyes of the general formula (I) are present in amounts of from 0.01 to 15% by weight, in particular in amounts of from 0.1 to 10% by weight, based on the dyestuff or the printing paste.
  • the extraction process at a pH of 3 to 7, in particular at a pH of 4 to 6 dyed.
  • the liquor ratio can be chosen within a wide range and is for example between 1: 3 and 1:50, preferably between 1: 5 and 1: 30. It is preferably dyed in an aqueous bath at temperatures between 40 and 105 0 C, optionally at a temperature up to 130 0 C under pressure, and optionally in the presence of conventional dyeing auxiliaries.
  • To increase the wet fastness of the dyed material can be removed in a post-treatment unfixed dye. This aftertreatment is carried out in particular at a pH of 8 to 9 and at temperatures of 75 to 80 ° C.
  • the material is introduced into the warm bath and this is gradually heated to the desired temperature and the dyeing process is completed.
  • the neutral salts which accelerate the removal of the dyes can also be added to the bath only after the actual dyeing temperature has been reached.
  • cellulose fibers are also excellent color yields and a very good color composition obtained by staying at Room temperature or elevated temperature, for example up to about 60 " 1 O, can be fixed by steaming or dry heat in a conventional manner.
  • the single phase for example, by printing with a sodium bicarbonate or other acid-binding agent-containing printing paste and subsequent steaming at
  • thermofixing by means of dry heat according to the usual thermofixing hot air is used from 120 to 200 0 C.
  • 101 to 103 0 C can also superheated steam and pressure steam of temperatures up to 160 0 C are used.
  • the acid-binding and the fixing of the dyes on the cellulose fibers causing agents are, for example, water-soluble basic salts of alkali metals and also alkaline earth metals of inorganic or organic acids or compounds which release alkali in the heat.
  • the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids may be mentioned, of the alkali metal compounds preferably the sodium and potassium compounds are meant.
  • Such acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium trichloroacetate, water glass or trisodium phosphate.
  • novel reactive dyes of the general formula (1) are characterized by high reactivity, good fixability, very good build-up capacity, as well as high light and perspiration light fastness. They can therefore be used by the Ausziehfärbeclar at low dyeing temperatures and require Pad-Steam process only short steaming times.
  • the degrees of fixation are high, and the unfixed portions can be easily washed out, the difference between the degree of exhaustion and the degree of fixation remarkably small, ie the Seifpetit is very low.
  • They are also particularly suitable for printing, especially on cotton, but also for printing on nitrogen-containing fibers, eg. As wool or silk or blended fabrics containing wool or silk.
  • the reactive dyes of the general formula (1) according to the invention are characterized in that non-fixed dye components can be washed out very easily on the fiber material after the dyeing process, without whitening, which is involved in the washing process, being soiled by the detaching dye. This results in advantages for the dyeing process, in which washing cycles and thus costs are saved.
  • the dyeings and prints prepared with the dyes of the general formula (1) according to the invention have, in particular on polyamides, high color strength and high fiber-dye binding stability in both the acidic and the alkaline range, furthermore good fastness to light and very good Wet fastness properties, such as washing, water, seawater, over-dyeing and perspiration fastness, as well as good plushing fastness, ironing fastness and rub fastness.
  • the present invention relates to the use of the abovementioned dyes of the general formula (1) in printing inks for digital textile printing by the ink-jet process.
  • the printing inks of the invention comprise one or more of the reactive dyes mentioned, for example in amounts of from 0.1% by weight to 50% by weight, preferably in amounts of from 1% by weight to 30% by weight and more preferably in amounts of 1 wt .-% to 15 wt .-% based on the total weight of the ink. It may also contain combinations of said reactive dyes with other reactive dyes used in textile printing.
  • a conductivity of 0.5 to 25 mS / m can be set by addition of electrolyte. Suitable electrolytes are, for example: lithium nitrate, potassium nitrate.
  • the dye inks according to the invention can be organic solvents with a
  • Suitable organic solvents are, for example
  • Alcohols e.g. As methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert. Butanol, pentyl alcohol, polyhydric alcohols z. B, 1, 2-ethanediol, 1, 2,3-propanetriol,
  • monoethylene glycol diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyl triglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, lower alkyl ethers of polyhydric alcohols, e.g.
  • B ethylene glycol monomethyl ether, ethylene glycol, diethylene glycol, diethylene, diethylene, diethylene glycol monohexyl ether, triethylene, triethylene or tripropylene, tetraethylene glycol monomethyl ether, tetraethylene, tetraethylene, propylene glycol, propylene glycol, propylene glycol, Tripropylenglykolisopropylether, polyalkylene such.
  • B. Polyethylene glycol monomethyl ether, polypropylene glycol glycerol ether, Polyethylenglykoltridecylether, Polyethylenglykolnonylphenylether, amines, such as. Example: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine, N-formylethanolamine, ethylenediamine,
  • Urea derivatives such as.
  • Amides such as For example: dimethylformamide, dimethylacetamide, acetamide, ketones or ketoalcohols, such as. B.: Acetone, diacetone alcohol, cyclic ethers, such as. B .; Tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, gamma-butyrolactone, epsilon-caprolactam, also sulfolane, dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethylsulfone, butadienesulfone, dimethylsulfoxide, dibutylsulfoxide, N-cyclohexylpyrrolidone , N-methyl-2-pyrrolidone, N-ethyl-pyrrolidone, 2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 1- (3
  • the printing inks of the invention may contain the usual additives, such as viscosity moderators to adjust viscosities in the range of 1, 5 to 40.0 mPas in a temperature range from 20 to 50 0 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.
  • Suitable viscosity moderators are rheological additives, for example:
  • polyvinylcaprolactam, polyvinylpyrrolidone and their co-polymers polyether polyol, associative thickener, polyurea, polyurethane, sodium alginates, modified galactomannans, polyether urea, polyurethane, nonionic cellulose ethers.
  • the inks of the invention can surface-active substances for the adjustment of surface tensions of 20 to 65 mN / m, which are optionally adjusted depending on the method used (thermal or piezo technology).
  • Suitable surface-active substances are, for example: surfactants of all kinds, preferably nonionic surfactants, butyldiglycol, 1,2-hexanediol.
  • the inks may still contain conventional additives such as fungicidal and bacterial growth inhibiting agents in amounts of from 0.01 to 1% by weight based on the total weight of the ink.
  • the inks can be conveniently prepared by mixing the components in water getting produced.
  • the dye inks according to the invention are suitable for use in inkjet printing processes for printing a wide variety of preprepared materials, such as silk, leather, wool, cellulosic fiber materials of all kinds and polyurethanes, and in particular polyamide fibers.
  • preprepared materials such as silk, leather, wool, cellulosic fiber materials of all kinds and polyurethanes, and in particular polyamide fibers.
  • Printing inks are also suitable for printing pretreated hydroxyl-containing or amino-containing fibers contained in blend fabrics, z.
  • blend fabrics, z As mixtures of cotton, silk, wool with polyester fibers or polyamide fibers.
  • the auxiliaries In contrast to conventional textile printing, in which the printing ink already contains all fixing chemicals and thickeners for a reactive dye, in the case of ink-jet printing the auxiliaries must be applied to the textile substrate in a separate pretreatment step.
  • the pretreatment of the textile substrate such as, for example, cellulose and cellulose regenerated fibers, as well as silk and wool, takes place before printing with an aqueous alkaline liquor.
  • Alkali such as sodium carbonate, sodium bicarbonate, sodium acetate, trisodium phosphate, sodium silicate, sodium hydroxide, alkali donors such as sodium chloroacetate, sodium formate, hydrotropes such as urea, reduction inhibitors such as sodium nitrobenzenesulfonates, as well as thickening agents, the flow of the To prevent motifs when applying the ink, these are, for example, sodium alginates, modified polyacrylates or highly etherified galactomannans. These pre-preparation reagents are coated with suitable applicators, such as a 2- or 3-roll pad, with non-contact
  • Spray technologies applied by foam application or with appropriately adapted inkjet technologies in a defined amount evenly on the textile substrate and then dried. After printing, the textile fiber material is dried at 120 to 150 ° C and then fixed.
  • the fixation of the ink jet prints prepared with reactive dyes can be carried out at room temperature, or with saturated steam, with superheated steam, with hot air, with microwaves, with infrared radiation, with laser or electron beams or with other suitable types of energy transfer.
  • the prints produced with the dye inks according to the invention have, especially on polyamide, a high color strength and a high fiber-dye bond stability in both the acidic and in the alkaline range, furthermore good light fastness and very good wet fastness properties, such as washing, water, seawater -, over-dyeing and perspiration, as well as a good pleating, ironing and rubbing fastness.
  • Parts by weight refer to parts by volume such as kilograms to liters.
  • the compounds described by formula in the examples are given in the form of the free acid. In general, however, they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and used in the form of their salts for dyeing.
  • the starting compounds and components mentioned in the following examples, in particular table examples, in the form of the free acid and components as such or in the form of their salts, preferably alkali metal salts can be used in the synthesis.
  • example 1 In a mixture of 400 ml of toluene and 100 ml of triethylamine are 187 g of 2,6-dichloro-4-methyl-nicotinonitrile (3-cyano-2,6-dichloro-4-methyl-pyridine) and 89 g of 3-methoxy-propylamine entered. The mixture is heated to 50 0 C, and stirred for 16 hours at this temperature.
  • the diaminopyridine of the formula (10-1) thus obtained is introduced into 100 ml of water together with 0.165 g of sodium tungstate dihydrate and 1 ml of ethanol and heated to 50 0 C. 15 ml of 35% hydrogen peroxide solution are added to this mixture within 6 hours.
  • the diaminopyridine of the formula (2-1) is obtained. The isolation is carried out after cooling by suction.
  • the diaminopyridine of formula (2-1 a) is stirred with methanol and added to a reaction mixture of a diazonium salt which is prepared from 8.9 g of 2-amino-5- (4-sulfophenylazo) -benzenesulfonic acid (D-44) by conventional Diazotization was obtained. With soda solution, the pH of the mixture is kept at 3.5 to 4.5 for about 2 hours and then adjusted to 6.5. It is isolated in the usual way by salting out with sodium chloride and suction and dried the resulting presscake. The product of the formula (1 -1 a) is obtained in the form of the disodium salt, written as the free acid:
  • the filtrate is adjusted to a pH of 10 to 11 with 20% sodium hydroxide solution, stirred for 30 minutes at this pH, adjusted to a pH of 6 to 6.5 with hydrochloric acid and evaporated.
  • the residue contains the product of (1 -1 c) in the form of the disodium salt, written as the free acid,
  • the dyeings are characterized by good fastness properties, in particular by good light and wet fastness.
  • reaction mixture contains the product of formula (2-2a).
  • reaction mixture can be used without further workup for the coupling with diazonium salts.
  • 20% saline solution is added and the precipitated solid is filtered off with suction, washed and dried.
  • the filtrate contains the compound of formula (2-2b) in the form of the sodium salt, written as the free acid.
  • the solution thus obtained (the filtrate) is adjusted to a pH of 10 to 1 l with 20% sodium hydroxide solution, stirred for 60 minutes at this pH, adjusted to a pH of 6 to 6.5 with hydrochloric acid and the precipitated solid is filtered off with suction, washed and dried. There is thus obtained a product containing the compound of the formula (2-2c).
  • the product of formula (2-2a) is added at a temperature of 15 to 20 0C to a reaction mixture of a diazonium salt which is composed of 12.5 g of 2-amino 5- (4-sulfo-phenylazo) -benzenesulfonic acid (D-44) was obtained by conventional diazotization.
  • the product thus obtained is added at a temperature of 10-15 ° C in 45 ml of 100% sulfuric acid (monohydrate) and stirred for 16 hours at this temperature.
  • the reaction mixture is discharged onto 300 g of ice, adjusted at a temperature of 0-5 0 C with 85 g of calcium carbonate to a pH of 6 and filtered.
  • the filtrate contains the product of the formula (1 -2b) in the form of the trisodium salt, written as the free acid,
  • the dyeings are characterized by good fastness properties, in particular by good light and wet fastness.
  • the dye of formula (1-2c) may also be obtained by coupling the diazonium salt of diglybaic acid (D44) to the coupler of formula (2-2c).
  • the product (2-3a) can also be obtained in the following manner: Half of the product Example 3, Formula (9-3) is introduced into 62 g of ethanolamine (2-aminoethanol) and heated to 105 to 120 0 C. At the end In the reaction, the reaction mixture contains the following compounds (Formula 10-3):
  • reaction mixture 50 ml of water, 100 ml of N-methylpyrrolidone, heated to 50 ° C., are added to the mixture 1.65 g of sodium tungstate.
  • Dihydrate, 240 ml of 30% hydrogen peroxide solution is added dropwise so that the temperature does not rise above 75 ° C and stirred at this temperature until completion of the reaction, about 5 hours.
  • the reaction mixture (406 g solution B) contains the compounds (2-3a). The reaction mixture can without further workup for the coupling with
  • Diazonium salts are used.
  • For the isolation of the product is with 20%
  • the solution thus obtained (the filtrate) is adjusted to a pH of 10 to 11 with 20% sodium hydroxide solution, stirred for 30 minutes at this pH, adjusted to a pH of 6 to 6.5 with hydrochloric acid and evaporated.
  • a product is thus obtained which contains the compounds of formula (2-3c) in the form of the sodium salts, written as free acids.
  • the product thus obtained is added at a temperature of 10 - 15 0 C in 60 ml of 100% sulfuric acid (monohydrate) and stirred for 9 hours at this temperature.
  • the reaction mixture is discharged onto 400 g of ice, adjusted at a temperature of 0 - 5 0 C with 1 15 g of calcium carbonate to a pH of 6 and filtered.
  • the filtrate contains the dyes of the formula (1 -3b) in the form of the tetrasodium salts, written as free acids,
  • Dyes of the formula (1-3b) can also be obtained by coupling the diazonium salt of the diglybaic acid to couplers of the formula (2-3b).
  • the solution of the dyes (the filtrate) is adjusted with 20% sodium hydroxide solution to a pH of 10 to 1 1, stirred for 30 minutes at this pH, adjusted to a pH of 6 to 6.5 with hydrochloric acid and evaporated.
  • Dyes of the formula (1-3c) may also be obtained by coupling the diazonium salt of the diglybaic acid to couplers of the formula (2-3c).
  • Example 3 Formula (2-3a) become a reaction mixture of the diazonium salt which consists of 25 g of 2- (4-amino-3-sulfophenyl) -2H-naphtho [1,2-d] [1, 2,3] triazole-6,8-disulfonic acid (Formula D48) was obtained by diazotizing in the usual manner.
  • the dyeings are characterized by good fastness properties, in particular by good light and wet fastness.
  • the solution of the dyes (the filtrate) is adjusted with 20% sodium hydroxide solution to a pH of 10 to 1 1, stirred for 30 minutes at this pH, adjusted to a pH of 6 to 6.5 with hydrochloric acid and evaporated.
  • the mixture thus obtained is adjusted to a pH of from 3 to 3.5 with hydrochloric acid, allowed to stand for about 16 hours, filtered off with suction, the resulting presscake is washed with water, suspended in water, filtered off with suction again and washed with water.
  • the obtained press cake contains the product of the following formula (11 -11).
  • the obtained press cake is dispersed in 300 ml of ice water.
  • the mixture is warmed to 30 0 C and treated with 1.65 g of sodium tungstate dihydrate.
  • reaction mixture 315 g of the reaction mixture thus obtained are added to a reaction mixture of the diazonium salt obtained from 8.93 g of 2-amino-5- (4-sulfophenylazo) benzenesulfonic acid (diglybaic acid) by diazotizing in the usual manner. With soda solution, the pH of the mixture is kept at 3.5 to 4.5 for about 4 hours and then adjusted to 6.5. The reaction mixture is filtered and evaporated. The residue thus obtained contains the product of formula (13-1a) in the form of the disodium salt, written as the free acid:
  • the product thus obtained is added at a temperature of 10-15 ° C in 90 ml of 100% sulfuric acid (monohydrate) and stirred for 2 hours at this temperature.
  • the reaction mixture is discharged onto 600 g of ice, adjusted at a temperature of 0-5 0 C with 170 g of calcium carbonate to a pH of 6 and filtered. Half of the filtrate is evaporated.
  • the residue contains the product of formula (13-1b) in the form of the tetrasodium salt, written as the free acid,
  • the dyeings are characterized by good fastness properties, in particular by good light and wet fastness.
  • the dyeings are characterized by good fastness properties, in particular by good light and wet fastness.
  • the compounds can be prepared in the following table:
  • 1 part of the dyestuff according to formula (1 -1 c) are dissolved in 2000 parts of water and 5 parts of sodium sulphate, 1 part of a leveling agent (based on a higher aliphatic amine condensation product and ethylene oxide) and 5 parts of sodium acetate are added.
  • a leveling agent based on a higher aliphatic amine condensation product and ethylene oxide
  • the pH is adjusted to 4.5 with acetic acid (80%).
  • the dyebath is heated to 50 ° C. for 10 minutes and then 100 parts of a wool fabric are added. The mixture is heated within 50 minutes to a temperature of 100 0 C and colored for 60 minutes at this temperature. Then allowed to cool to 90 0 C and removes the Klarbegut.
  • the wool fabric is washed with warm and cold water, then spun and dried. It will get a red color with good light and wet fastness, as well as good Faseregaltician.
  • 1 part of the dyestuff according to formula (1 - 2c) is 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 5 parts of sodium acetate is added.)
  • the pH is then adjusted with acetic acid (80 %) is set to a value of 5.
  • the dyebath is heated for 10 minutes at 50 0 C., and then 100 parts of a polyamide fabric was added.
  • the mixture is heated over 50 minutes to a temperature of 1 10 0 C, and dyeing is 60 minutes This temperature is then allowed to cool to 60 ° C. and the product is removed.
  • the polyamide fabric is washed with warm and cold water, soaped and then spun and dried.
  • Dyeing Example 3 2 parts of a dye obtained according to formula (1 -3b) and 50 parts
  • Sodium chloride is dissolved in 999 parts of water and 5 parts of sodium carbonate, 0.7 part of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent added.
  • this dyebath there One 100 g of a cotton fabric.
  • the temperature of the dyebath is initially maintained at 25 ° C. for 10 minutes, then raised to final temperature (40-80 ° C.) in 30 minutes, and this temperature is maintained for a further 60-90 minutes. Thereafter, the dyed fabric is first rinsed with drinking water for 2 minutes and then with e-water for 5 minutes. Neutralize the dyed fabric at 40X; in 1000 parts of an aqueous solution containing 1 part of 50% acetic acid for 10 minutes. With E-water is rinsed at 70 0 C and then soaped for 15 minutes with a detergent, rinsed again and dried. This gives a strong red color with very good fastness properties.
  • a textile fabric consisting of mercerized cotton is padded with a liquor containing 35 g / l of sodium carbonate, 100 g / l of urea and 150 g / l of a low-viscosity Na alginate solution (6%) and then dried.
  • the fleet intake is 70%.
  • aqueous ink containing 2% of the dye according to Example (1 -3c) 20% sulfolane 0.01% Mergal K9N 77.99% water with a drop-on-demand (bubble jet) ink is applied to the textile pretreated in this way. Jet print head printed. The print is completely dried. The fixation takes place by means of saturated steam at 102 0 C for 8 minutes. Subsequently, the pressure is rinsed warm, subjected to hot water at 95 0 C a fastness wash, rinsed warm and then dried. This gives a bluish red print with excellent use fastness.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)
  • Pyridine Compounds (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

L'invention se rapporte à des colorants réactifs de formule générale (I) dans laquelle R<SUP>1</SUP> à R<SUP>5</SUP>, Ar, n, Y et D sont tels que définis dans les revendications 1 et 2. Cette invention concerne en outre des procédés de production de ces composés, ainsi que leur utilisation pour colorer et imprimer un matériau comportant des groupes carbonamide, des groupes amino, et des groupes hydroxy.
EP06806725A 2005-04-26 2006-04-19 Colorants reactifs azo, leurs procedes de production, et leur utilisation Withdrawn EP1877495A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005019333A DE102005019333A1 (de) 2005-04-26 2005-04-26 Reaktive Azofarbstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung
PCT/EP2006/061657 WO2007006594A2 (fr) 2005-04-26 2006-04-19 Colorants reactifs azo, leurs procedes de production, et leur utilisation

Publications (1)

Publication Number Publication Date
EP1877495A2 true EP1877495A2 (fr) 2008-01-16

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US (1) US20080289124A1 (fr)
EP (1) EP1877495A2 (fr)
CN (1) CN101142285A (fr)
DE (1) DE102005019333A1 (fr)
TW (1) TW200637890A (fr)
WO (1) WO2007006594A2 (fr)

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JP5609229B2 (ja) * 2009-04-27 2014-10-22 住友化学株式会社 化合物及び該化合物を含む着色感光性樹脂組成物
US20130128325A1 (en) * 2009-12-16 2013-05-23 Rafael Artasanchez Bautista Process for obtaining a variable high security hologram and its applications

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DE3025904A1 (de) * 1980-07-09 1982-02-11 Hoechst Ag, 6000 Frankfurt Wasserloesliche azoverbindungen, verfahren zu ihrer herstellung und ihre verwendung als farbstoffe
DE59309202D1 (de) * 1992-07-23 1999-01-21 Ciba Geigy Ag Reaktivfarbstoffe, Verfahren zu deren Herstellung und deren Verwendung
ES2135438T3 (es) * 1992-12-07 1999-11-01 Basf Ag Mezclas de colorantes que contienen colorantes azoicos con un componente de copulacion de la serie de diaminopiridina.

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See references of WO2007006594A3 *

Also Published As

Publication number Publication date
CN101142285A (zh) 2008-03-12
DE102005019333A1 (de) 2006-11-02
TW200637890A (en) 2006-11-01
US20080289124A1 (en) 2008-11-27
WO2007006594A2 (fr) 2007-01-18
WO2007006594A3 (fr) 2007-11-29

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