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
  • C09B62/44—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
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/40—Nitrogen atoms
  • C07D251/54—Three nitrogen atoms
  • C07D251/70—Other substituted melamines
• • 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
  • C09B43/00—Preparation of azo dyes from other azo compounds
  • C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
  • C09B43/136—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents
  • C09B43/16—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents linking amino-azo or cyanuric acid residues
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
  • D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/02—Material containing basic nitrogen
  • D06P3/028—Material containing basic nitrogen using reactive dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/02—Material containing basic nitrogen
  • D06P3/04—Material containing basic nitrogen containing amide groups
  • D06P3/10—Material containing basic nitrogen containing amide groups using reactive dyes

Definitions

• the resent invention relates to compounds of the formula (1 )
• the present invention further relates to a process for the preparation of the compounds of the formula (1 ) and intermediates used for manufacturing of dyestuffs of the formula (1 ).
• EP 623.655 describes dyes of the general formula
• D1 is a radical of a dye chromophore
• X is halogen, substituted pyridine or optionally substituted amino, hydroxyl, alkoxy or alkylthio - preferably halogen
• D is a radical of the formula
• Z is benzene or naphthalene radical carrying a fibre reactive group of the vinylsulfonyl type.
• EP 957,137 describes mixtures of d es of the general formulae (1 ) and (2)
• M is hydrogen, ammonium, an alkali metal or the equivalent of an alkaline earth metal
• R1 is hydrogen or sulfo
• R2 is hydrogen or sulfo
• X1 and X2 are each fluorine, chlorine, amino, which may be mono- or disubstituted by lower alkyl or optionally substituted aryl and one of the radicals possesses a group of the formula -S02-Y1 or - S02-Y2, where Y1 and Y2 are each vinyl or ethyl substituted in the beta -position by an alkali-eliminable grouping, or X1 and X2 are each optionally substituted morpholino or pyrimidino, cyanoamino, hydroxyl, lower alkoxy or optionally substituted aryloxy and where the groups -S02-Y1 and -S02-Y2 are attached to the benzene nucleus meta or para to the azo or amino group.
• the present invention discloses novel fibre-reactive dyes which are suitable for dyeing from aqueous bath and printing of fibre materials containing cellulose, polyamide or protein fibre materials, and blends containing such fibre materials.
• the dyes of the present invention carrying two reactive groups of the vinylsulfone type overcome these limitations have excellent fixation yield and excellent build-up. They can achieve very deep shades with very good fastness to washing, water, acid and alkaline perspiration (contact fastness).
• Water soluble dyestuffs having two vinylsulfone reactive groups in the form of free acid of the formula (1 ) and salts thereof
• X is -NHCN, -NHR, -N (CH 3 ) R, -O- R, or - or X is a heterocyclic radical of the formula — W
• R is selected from C1 -C6-Alkyl, which is substituted by at least one sulfo, sulfato, phosphate, thiosulfato or carboxy substituent, and optionally by further substituents such as hydroxy;
• R a is Hydrogen or C1 -C4-alkyl, which is non-substituted or may be substituted by halogen, hydroxyl, cyano, alkoxy, carboxy and sulfo,
• R b has one of the meanings of R a ,
• K 2 has one of the meanings of K 1 ;
• benzene or naphthalene radical which is non-substituted or substituted by one or more substituents selected from sulfo, C1 -C4 alkyl, C1 -C4 alkoxy or halogen,
• D2 has one of the meanings of D1 ,
• Y is Vinyl or CH2CH2-L in which L is a leaving group selected from groups such as sulfato, acetato, halogen, such as chloro or bromo, phosphate, thiosulfato, acyloxy, such as acetoxy or phenoxy,
• a process for manufacturing dyestuffs of the formula (1 ), by step-wise condensing monoazo dyestuffs of the formula NHRa and Y0 2 S-D 2 N N-K2NHR b with compounds of the formula Hal 2 cyX ,wherein Hal is chloro or fluoro , cy is 1 ,3,5-triazinyl and X has one of the above meanings.
• a process for manufacturing asymmetrical dyestuffs of the formula (1 ), by first synthesizing an intermediate of the formula Y0 2 S-D 1 N N-K1 NR a -cyXHal, then condensing with K2NR b and finally coupling with diazotized Y0 2 S-D 2 NH 2 .
• the dyestuffs of the present invention are water soluble yellow, orange, brown and red dyestuffs carrying two vinylsulfone reactive groups which are in the form of the free acid of the formula 1 )
• K 2 has independently of the meaning of Ki one of the meanings of K 1 ;
• X is -NHCN, -NHR, -N(CH 3 ) R, -O- R , or -S- R wherein R is CrC 6 -alkyl, preferably CrC 3 , which is substituted by at least one sulfo, sulfato, phosphato, thiosulfato or carboxy substituent, and optionally by further substituents such as hydroxy, or a heterocyclic radical of the formula
• W has one of the meanings of R, preferably ⁇ -sulfatoethyl, and in particular, X is preferably cyanamino, 2-sulfoethylamino, N-methyl- 2-sulfoethyl- amino, 2-sulfatooethylamino, carboxymethylthio, carboxyethyloxy or a radical of the formula
• R a is hydrogen or CrC 4 -alkyl, which is non-substituted or may be substituted by halogen, hydroxyl, cyano, alkoxy, carboxy and sulfo, preferably R a is hydrogen or methyl,
• R b has independently of R a one of the meanings of R a
• Y is vinyl or CH 2 CH 2 L, wherein L is a leaving group which is split off under alkaline conditions, such as sulfato, acetato, halogen, such as chloro or bromo, phosphate, thiosulfato, acyloxy, such as acetoxy or phenoxy, preferably Y is vinyl or ⁇ -sulfatoethyl, is a benzene or naphthalene radical of the formula (2a) or (2b) which may be non- substituted or substituted by one or more substituents sulfo, Ci -C 4 -alkyl, Ci-C 4 -alkoxy, or halogen,
• D 2 has independently of the meaning of Di one of the meanings of Di .
• Suitable radicals Y include vinyl, 2-sulfatoethyl, 2-chloroethyl, 2-bromoethyl, 2- acetoxyethyl, 2-phenoxyethyl, 2-phosphatoethyl, 2-thiosulfatoethyl.
• Y is vinyl or 2-sulfatoethyl.
• formula (2a) in D1 independent of D2 is one of the following radicals
• Y is Vinyl or ⁇ -sulfatoethyl
• formula (2b) in D1 independent of D2 is one of the following radicals
• K NR a - is preferably a radical of the formula (3a), (3b) or (3c) of the benzene or series or a radical (4) of the naphthalene series,
• R 0 is hydrogen or methyl, preferably hydrogen
• Ri is hydrogen, methyl, or ethyl, preferably hydrogen
• R 2 is amino or methyl
• r 0-1
• K 2 -NR b has independently of K NR a one of the meanings of K NR a, wherein the radicals R 0 , Ri , R2 and r have one of the above meanings.
• formula (3a) is one of the following radicals
• formula (3b) is the following radical
• formula (3c) is one of the followin radicals
• formula (4) is ne of the following radicals
• radicals X include cyanamino, sulfomethylamino-, 2- sulfoethylamino, N-methyl-2-sulfoethylamino, 3-sulfopropylamino-, 2-sulfato-ethylamino-,
• the reactive group ⁇ -sulfatoethylsulfonyl is drawn in the form of its sulfuric acid form but can likewise be the alkali metal salt thereof, especially sodium salt, or it can be in the form of vinylsulfonyl to which it is easily converted upon exposure to alkaline medium, and the sulfo groups are drawn in the form of its sulfuric acid form as well, but can likewise be the alkali metal salt thereof, especially sodium salt.
• This illustration form is used in all further structures drawn of preferred embodiments or preferred radicals
• especially preferred dyestuffs for dyes of the present invention are the dyestuffs of the formula (1 .1 ), (1 .2), (1 .3), (1 .4), (1 .5) and (1 .6)
• R1 is hydrogen or methyl, preferably hydrogen
• R2 ' is methyl or amino
• X is Cyanamino, N(CH3)-CH 2 CH 2 -S0 3 H , NH-CH 2 CH 2 -S0 3 H, S-CH 2 -COOH, 0-( CH 2 ) 2 - COOH, or a radical of the formula
• Y is Vinyl or ⁇ -sulfatoethyl.
• dyestuffs (1.1) to (1.6) such dyestuffs containing at least one sulfo group in the radicals and K 2 NR b are especially preferred.
• the dyes of the formula (1.1a), (1.1. b) and (1.1. c) are especially preferred.
• examples for dyes of the present invention are the following dyestuffs
• the novel dyestuffs can be in the form of the free acid or their salts, preferably in the form of the salts, especially the alkali metal and alkaline earth metal salts, and in particular in the form of their sodium, potassium or lithium salts.
• the novel dyestuffs are preferably used in the form of their alkali metal salts for dyeing and printing fibre materials.
• radicals Q1 and Q2 are independent from each other amino or hydroxy, preferably amino, Ro is hydrogen or methyl, preferably hydrogen, and X has one of the meanings as defined above, are also part of the present invention. These intermediates are suitable as coupling components in the manufacturing of the dyestuff of the present invention.
• the present invention also relates to different processes for manufacturing of the novel dyestuffs of formula (1 ) (wherein cyX stands for 2-X-4, 6-triazinyl-) such as:
• the dyes of the present invention can be preferably prepared by different methods involving the following steps:
• the K1 -NR a -cyX-Hal is prepared as described under A3 or A6.
• the diazotization of the aromatic amines D NH 2 and D 2 NH 2 used in the methods a) to e) are carried out by generally known methods, in presence of acid, in particular hydrochloric acid or sulfuric acid, and sodium nitrite at a temperature of -5 to 25 °C, preferably at a temperature of 0-5 °C.
• Aromatic amines of the formula D NH 2 and D 2 -NH 2 are known form various publications, such as the German patent applications Nos. 1.278.041 , 1 .276.842, 1 .150.163, 1 .126.542, 1 .153.029.
• diazo compounds of the aromatic amines of the formula Di-NH 2 and D 2 -NH 2 are examples.
• novel dyestuffs can be in the form of the free acid or in the form of their salts. They are preferably in the form of the salts, especially the alkali metal and alkaline earth metal salts, and in particular in the form of their sodium, potassium or lithium salts.
• the novel dyestuffs are preferably used in the form of their alkali metal salts for dyeing and printing fibre materials.
• the present invention further provides a process for dyeing from aqueous bath and printing of fibre materials containing hydroxyl and/or amino groups with the dyes of the present invention.
• cellulose natural cellulose fibres such as cotton, linen or hemp, especially cotton, and regenerated cellulose such as viscose or Lyocell, polyamide fibres such as nylon 6, nylon 6.6 or protein fibres such as wool or silk are preferred fibre materials.
• the dyes are also suitable for dyeing and printing of fibre blends containing the mentioned cellulose, polyamide or protein fibre materials.
• the dyes of the invention can be applied to and fixed on the fibre material in various ways, in particular in the form of aqueous dye solutions and print pastes. They are suitable for known application techniques which are established for the application of reactive dyes, in particular exhaust method, padding methods, whereby the material is impregnated with aqueous, salt containing or salt free solutions of the dyes, and fixed after alkali treatment or in presence of alkali with or without heating, and printing methods, conventional or digital (ink jet) printing. After fixing, the dyeing and prints are rinsed and thoroughly washed with cold or hot water containing auxiliary agents such as detergents or surfactants that promote the wash-off of unfixed portions.
• auxiliary agents such as detergents or surfactants that promote the wash-off of unfixed portions.
• alkali used for fixation examples include alkali hydroxide, alkali carbonate, alkali silicate, of which sodium hydroxide, sodium carbonate, sodium silicate are in particular preferred.
• the amounts wherein the dyes are applied in the dye baths can vary according to the desired depth of shade, generally amounts of 0.01 to 10 % per weight of fabric are suitable, in particular 0.2 to 8%.
• the dye bath may contain additions of auxiliaries such as inorganic salt, preferably sodium chloride or sodium sulfate, to support the exhaustion of the dyes onto the fibre material, and in padding process urea, and in printing applications thickening pastes such as alginate thickenings.
• auxiliaries such as inorganic salt, preferably sodium chloride or sodium sulfate, to support the exhaustion of the dyes onto the fibre material, and in padding process urea, and in printing applications thickening pastes such as alginate thickenings.
• the preferred procedure is dyeing from an aqueous batch, in presence of 20-100 g/L salt, sodium chloride or sodium sulfate, and a liquor ratio of 1 :2 to 1 :50, preferably 1 :3 to 1 :30, at a dye bath pH of 7-13, preferably 9-1 1 , and a temperature of 40-90, preferably 45-65 ⁇ ⁇ .
• the dyeing obtained with the dyes of the present invention has excellent fixation yield and excellent build-up.
• the obtained dye-fibre bond is of high stability not only in the acid but also in the alkaline range, also good light fastness and very good wash fastness, even in deep shades, as well as good contact fastness to water, and perspiration.
• the dyeing obtained with the dyes of the present invention are dischargeable and can be applied in discharge printing.
• Example 1 The relationship between the parts by weight quoted in the examples and parts by volume is the same as between kilogram and liters. The percentages are by weight unless stated otherwise.
• Example 1 The relationship between the parts by weight quoted in the examples and parts by volume is the same as between kilogram and liters. The percentages are by weight unless stated otherwise.
• Example 1 The relationship between the parts by weight quoted in the examples and parts by volume is the same as between kilogram and liters. The percentages are by weight unless stated otherwise.
• Example 1 The relationship between the parts by weight quoted in the examples and parts by volume is the same as between kilogram and liters. The percentages are by weight unless stated otherwise.
• the dyestuff is isolated by adding potassium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C.
• This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• Example 2
• reaction slurry is filtered, washed with warm water. Then the wet cake is dispersed in 2000 parts per volume of water, to which is charged 722 parts by weight of freshly diazotized 2-Sulfo-4-(B-sulfatoethylsulfonyl)phenylamine in 2000 parts per volume of water.
• Cou lin is carried out at pH 5-6 and 0-5 °C to yield a dyestuff of the formula
• the dyestuff is isolated by spray drying in the usual manner. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• the dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C.
• This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• comparative dye 1 vs example 3 of the present invention surprisingly exhibits superior colour strength although one fibre reactive group has been removed.
• the dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C.
• This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• Golden yellow (436 is obtained.
• the dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• Golden yellow ( ⁇ max 430nm) is obtained.
• the dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• Golden yellow ( ⁇ max 432 nm) is obtained.
• the dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• the reaction slurry is filtered, washed with warm water. Then the wet cake is dispersed in 2000 parts per volume of water, to which is charged 722 parts by weight of freshly diazotized 2-Sulfo-4-(B-sulfatoethylsulfonyl) phenylamine in 2000 parts per volume of water.
• the azo coupling is carried out at pH 6.5-7 and 0-5 °C over a period of 4h.
• the dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• the following table illustrates more examples of the formula which can be prepared in a similar manner as in examples 1 -6 by using the respective intermediate compounds.
• the dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C.
• This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• the following table illustrates more examples which can be prepared in a similar manner as in example 30 by using the respective intermediate compounds.
• the dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C.
• This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades
• the dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• the dyestuff is isolated by adding sodium chloride, stirred for 1 h at 20-25 °C, precipitated, then filtered, washed with several portions of ice water and dried in vacuum at 60 °C.
• This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• the dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• the dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• the dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• the dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• the dyestuff is isolated by spray drying. This dyestuff is particularly suitable for dyeing of cotton or viscose fibres in medium to deep shades.
• 100 parts per weight of cotton fabric is padded with a padding liquor, applying a liquor pickup of 70% per weight of fabric, in a freshly prepared padding liquor containing 1000 parts of water, 25 parts per weight of the dyestuff of example 2, 30 parts per weight of sodium carbonate and 10 parts per weight of sodium hydroxide 50% solution.
• the padded fabric is then rolled, covered to keep it wet, and stored for a period of 16 to 24 h. Finally the fabric is rinsed and soaped in the same manner as outlined in dyeing example 1 . An orange dye with good fastness properties is obtained.

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