Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/20—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a pyrimidine ring
  • C09B62/24—Azo dyes
  • C09B62/25—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
  • C09B62/002—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the linkage of the reactive group being alternatively specified
  • C09B62/006—Azodyes
  • C09B62/01—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
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
  • C09B62/08—Azo dyes
  • C09B62/09—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
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/36—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to some other heterocyclic ring
  • C09B62/40—Azo dyes
  • C09B62/41—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
  • C09B62/4401—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
• • 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
  • C09B62/4401—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
  • C09B62/4424—Azo dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
  • C09B62/503—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

Definitions

• the present invention is in the field of reactive dyes.
• Reactive dyestuffs are dyestuffs which can be covalently bound via so-called reactive anchors to fibrous materials which have hydroxyl or amino groups. Most of the available reactive dyes are mainly suitable for dyeing cotton, only a few for other substrates such as polyamide, wool or silk. This is especially true for the dyeing of leather, where the commercially available reactive dyes have poor drawability and low Fixierausbeuten.
• dyes used today to dye leather are anionic dyes which can be assigned to the acid dyes, direct dyes or metal complex dyes (see, for example, K. Eitel in H. Herfeld (ed.): The Leather Library, Vol , Umschau Verlag, Frankfurt 1 987. G. Otto: The Dying of the Leather, Roether Verlag, Darmstadt 1962. Color Index, 3rd ed, Lund and Humphreys, Bradford - London 1 971 - 1 976.). Since these dyes are not covalently bound to the substrate, it can come under extreme conditions for the separation of the dyes from the leather.
• EP 0 71 6 130 A1 and EP 1 035 171 A1 disclose polyazo dyes which may also contain or contain reactive agents and which are also suitable for dyeing leather, without, however, solving the mentioned problems ,
• Reactive dyes have these properties and the described technical
• the present invention thus relates to polyazo dyes of the general formula I.
• T is a radical of the general formula II
• B is a bridge member of the formula -NH-, -CO-, -SO 2 -,
• -CH CH-, -CH 2 CH 2 -, -NH-CO-, -NH-SO 2 -, -SO 2 -NH-SO 2 - or a direct bond;
• R 6 , R 7 , R s and R 9 are each independently hydrogen, -SO 3 M,
• Aikyl distrin is substituted, di- (C r C 12 ) alkylamino, which is optionally substituted in the alkyl groups, optionally substituted
• T is a radical of general formula III wherein R 8 , R 7 , s and t are as defined above; R 1 and R 2 are hydrogen, amino or hydroxy, where not both radicals
• Amino and not both radicals may be hydroxy;
• M is hydrogen, an alkali metal or the equivalent of an alkaline earth metal;
• x is the number O, 1 or 2;
• R 3 and R 4 independently of one another have one of the meanings of R 5 or
• R 5 is hydrogen, OR 16 or -NR 17 R 18 , wherein
• R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently
• r is the number 1 or 2, with the exception of polyazo dyes in which r is the number 2, R 5 and one of the radicals R 3 and R 4 are amino and the other of the radicals R 3 and R 4 is -COOM, -COOR 10 , -CONR 11 R 12 or -CO-R 16 .
• Aryl groups Ar 1 and Ar 2 are preferably phenyl and naphthyl. If these are substituted, they carry 1, 2 or 3 substituents from the series -SO 3 M, hydroxy, amino, (C 1 -C 4 ) -alkylamino, DHCrCJ-Alkylami ⁇ o, nitro, (C r C 4 ) alkyl , (C 1 -CJ -alkoxy, (C r C 4> -AlkyI-SO 2 -., -C00M, -NHCOCH 3, and halogen the listed (C ⁇ can -CJ-alkyl groups may also be substituted, for example by Hydroxy, vinyl, phenyl, -CN or -COO (C 1 -C 4 -alkyl).
• At least one of Ar 1 and Ar 2 also carries a fiber-reactive group.
• fiber-reactive groups are used in the context of the present invention Understood groups that can form covalent bonds with hydroxyl- and / or carboxamido-containing materials, ie about with the hydroxy groups of cellulose materials or the carbonamide groups of wool, leather or polyamide. Such groups are known to those skilled in the art and described in detail in the literature.
• preferred fiber-reactive groups are heterocyclic groups of the formulas 1, 2 and 3
• FT represents hydrogen, phenyl or (C r C 4) alkyl
• X 1 to X 3 independently of one another are hydrogen, cyano or halogen, with the proviso that at least one radical X 2 or X 3 is halogen, X 4 is chlorine or fluorine,
• X 5 is a group of the general formula -N (R b ) -YR ', wherein R b is hydrogen, phenyl or (C r C 4 ) -alkyl; S
• Y is (C 1 -Cg) -alkyl, which may also be interrupted by -O-, or a group of the formula
• Z are, for example, chlorine, sulfato, thiosulfato, phosphato or (C z -C 5 ) alkanoyloxy, such as acetyloxy, and sulfobenzoyloxy.
• Z is sulfato.
• a (C r C 4 ) -alkyl group which is a substituent R 6 to R 18 can be straight-chain and branched and is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec Butyl or tert-butyl.
• R 6 to R 18 can be straight-chain and branched and is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec Butyl or tert-butyl.
• Halogen is preferably fluorine, chlorine or bromine.
• An alkali metal for M is preferably lithium, sodium or potassium.
• An equivalent of an alkaline earth metal for M is preferably one equivalent of calcium.
• Preferred polyazo dyes according to the invention are those of the general formula I in which T is a group of the general formula II. It is particularly preferred if B is -NH-, -NH-CO- or -NH-SO 2 - stands.
• polyazo dyes according to the invention are represented by the general formula Ia
• Ar 1 , Ar 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , M, r, s, t, u and v are as defined above;
• B is -NH-, -NH-CO- or -NH-SO 2 -; and one of R 1 and R 2 is hydroxy and the other is amino, and
• R 5 is OR 16 or -NR 17 R 18 , wherein R 16 , R 17 and R 18 are as indicated above
• Ar 1 , Ar 2 , R 3 , R 4 , M and r are as defined above;
• R 5 is OR 16 or -NR 17 R 18 wherein R 18 , R 17 and R 18 are as defined above.
• the compounds of the general formula I can be prepared by reacting compounds of the general formulas IV to VIIJ
• Ar 1 , Ar 2 , R 1 to R 5 , T, M and x are as defined above, are synthesized in diazotization and coupling reactions in any desired order.
• one mole equivalent of a compound of general formula IV in the usual way with nitrites for example
• polyazo dyes of the general formula I according to the invention in which r is 1, can be obtained by the following further variant.
• 1 to 3 molar equivalents of a diazotized compound of the general formula V with a coupling component of the general formula VIII to the compound of general formula XII 1 to 3 molar equivalents of a diazotized compound of the general formula V with a coupling component of the general formula VIII to the compound of general formula XII
• This compound is then reacted with a diazonium salt obtained by reacting a diazotised compound of the general formula IV with a coupling component of the general formula VI and reacting the resulting intermediate with a tetrazotised compound of the general formula VII.
• the compounds of the general formulas VI preferably have the following structures:
• the compounds of the general formulas VII preferably have the following structures:
• the general formulas VIII are preferably the following structures:
• the polyazo dyes according to the invention have valuable technical properties. They are used for dyeing or printing hydroxyl- and / or carboxamido-containing materials, for example in fiber form, in the form of fabrics, such as paper and leather or films, such as polyamide, or in the mass, such as polyamide and polyurethane. Also, the resulting in the synthesis of solutions of the polyazo dyes according to the invention, optionally after addition of a buffer substance, optionally after concentration or dilution, directly as a liquid preparation of färberische ⁇ use can be supplied. Hydroxy-containing materials are those natural or synthetic Origin, such as cellulose 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 as well as chemically modified cellulose fibers, such as aminated cellulose fibers or fibers, as described, for example, in WO 96/37641 and WO 96/37642 and in EP-A-0 538 785 and EP-A-0 692 559.
• Carbonamidenburgives include synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other T ⁇ erhaare, silk, leather, polyamide-6,6, polyamide-6, polyamide-1 1 and polyamide-4.
• the present invention thus also relates to the use of the polyazo dyes according to the invention for dyeing or printing these materials or processes for dyeing or printing such materials in per se conventional procedures in which one uses a polyazo dyes erfi ⁇ dungswashen as a colorant.
• the polyazo dyes according to the invention are preferably used for dyeing wool, polyamides and leather.
• 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 based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid and / or a Aminonaphthalinsulfonklare or based on a reaction product of, for example, stearylamine with ethylene oxide.
• the polyazo dyes according to the invention are 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 in order to achieve high color depths, the full reactive bond between the dyes of the invention ⁇ dye mixtures 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 of other natural polyamides or of synthetic polyamides. As a rule, the material to be colored becomes!
• the dyebath then adjusted to the desired weakly acid, preferably weakly acetic acid, pH and the actual dyeing at a temperature between 60 and 98 0 C.
• the dyeings can also be carried out at boiling temperature or in closed dyeing apparatus at temperatures up to 106 0 C. Since the water solubility of the polyazo dyes according to the invention is very good, they can also be used with advantage in conventional continuous dyeing processes.
• the color intensity of the dye mixtures according to the invention is very high.
• the process for dyeing leather is carried out in several steps known to those skilled in the art, which are preparing the leather, such.
• the actual dyeing and post-processing steps such as washing, stretching and cleats included.
• the coloring of the leather takes place from an acidic environment.
• the dyebath z.
• As formic acid or acetic acid or mixtures thereof and their Sodium salts are added to adjust the desired pH.
• the usual tools used in leather processing can be used.
• the polyazo dyes of the invention are dyed from acid dyebath at a pH of about 3.5 to 4.5 at temperatures of 40, 60 or 80 0 C, wherein the fixation of the dye is carried to the substrate.
• the solution of the polyazo dye of the general formula I used has a pH of less than 7 and is obtained without the addition of alkali, e.g. Soda or caustic soda, used for coloring the substrates.
• alkali e.g. Soda or caustic soda
• Particular preference is given to dyeing at pH values of 2 to 5, in particular at pH values of 3 to 5.
• Parts by weight refer to parts by volume such as kilograms to liters.
• the product is included as a main component.
• the product is obtained as a dark powder, which dyes wool and polyamide in olive green and cow leather in black shades with good general authenticity. The dye draws very well on the substrate and has good Ablbücherecht phenomenon eg solvent fastness.
• EXAMPLE 2 a) 32 parts of 1-amino-8-hydroxy-3,6-disulfonic acid are introduced into the solution obtained according to Example I f, the pH of the solution being 1 to 2 by the addition of 1 5% sodium carbonate solution is held. It is stirred for 360 minutes, during which time slowly heated to 35 0 C. Thereafter, it is stirred until complete coupling, cooled to 25 0 C and the pH of the solution by adding 1 5% sodium carbonate solution to 4.5 - 5.5 placed.
• Phenylenediamine The pH of the reaction mixture is kept at 8-8.5 by addition of 25% strength by weight aqueous sodium hydroxide solution and stirred until complete coupling. After completion of the coupling, the pH is adjusted by addition of 25 wt .-% tger aqueous sodium hydroxide to 10 - 1 1, stirred at 20 - 25 ° C for 60 minutes and by addition of 20% hydrochloric acid, a pH of 9 - 10 set.
• the dye obtained is in the usual manner precipitated by adding sodium chloride.
• the suspension obtained is filtered off with suction.
• the resulting filter cake is stirred in 450 parts of water and adjusted by the addition of 20% hydrochloric acid pH 6-7.
• the suspension obtained is suction filtered and the filter cake dried at 50 0 C.
• a compound is obtained which is in the form of the free acid of the formula
• the product is a dark powder, which stains cow leather in black tones with good fastness.
• Example 2d The product obtained according to Example t e is described in Example 2d
• Example 1 a was obtained according to the method described in Example 1 a.
• the resulting dye is precipitated in the usual manner by adding sodium chloride.
• the suspension obtained is suction filtered and the filter cake dried at 5O 0 C.
• the product is obtained as a dark powder, which dyes wool and polyamide in olive shades and leather in black shades with good fastness properties.
• the dye draws very well on the substrate and has good Abletteecht phenomenon eg solvent fastness.
• the mixture corresponds, as a dark powder, which dyes wool and polyamide in olive shades and cowhide in black shades with good fastness properties.
• the mixture contains components which correspond to the components specified in Examples 1 to 3.
• Example 2d The product obtained according to Example 1 e is described in Example 2d
• Example 1 a was obtained according to the method described in Example 1 a.
• the dye obtained is in the usual way by adding Sodium chloride like.
• the suspension obtained is suction filtered and the filter cake dried at 5O 0 C.
• a mixture is obtained which, in the form of the free acids, dyes of the formulas
• the mixture contains components which correspond to the components specified in Examples 1 to 3.
• Example 2d The product obtained according to Example 1 e is described in Example 2d
• the resulting dye is precipitated in the usual manner by adding sodium chloride.
• the suspension obtained is suction filtered and the filter cake dried at 50 0 C.
• the mixture corresponds, as a dark powder, which dyes wool and polyamide in olive shades and cowhide in black shades with good fastness properties.
• the mixture contains components which correspond to the components specified in Examples 1 to 3.
• Example 8 Treating the product obtained according to Example 8 in the manner with sodium hydroxide solution that one stirs a solution in water thereof at pH 10 to pH 1 1 two hours at room temperature and then the pH is adjusted to 7 with hydrochloric acid and the reaction mixture is evaporated, then you get a product of
• the leather also colors in green tones.
• the retanning is carried out in 250 parts of water at a temperature of 40 0 C with 5 parts of a commercially available synthetic tanning agent.
• the leather is tumbled for 45 minutes in the Nachgerb grindkeit, removed and washed with water.
• 0.045 parts of the dye to be dyed according to one of the preceding examples are dissolved in 300 parts of water, added to 15 parts of leather and adjusted to a pH of 4 with a buffer. While the leather is tumbling in the dyeing liquor, is heated to 8O 0 C within 20 minutes, held for 20 minutes at this temperature, heated in another 15 minutes at 100 ° C and held the temperature for 45 minutes. The mixture is then cooled to 4O 0 C and removed the leather to the dyebath. Then the leather is rinsed cold, stretched, dried and placed.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Coloring (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
• Thiazole And Isothizaole Compounds (AREA)
• Polyamides (AREA)

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