GB2162193A - Reactive disazo dyes with monochlorotriazinyl groups - Google Patents

Reactive disazo dyes with monochlorotriazinyl groups Download PDF

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GB2162193A
GB2162193A GB08514298A GB8514298A GB2162193A GB 2162193 A GB2162193 A GB 2162193A GB 08514298 A GB08514298 A GB 08514298A GB 8514298 A GB8514298 A GB 8514298A GB 2162193 A GB2162193 A GB 2162193A
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amino
reactive dye
formula
dye according
triazine
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GB8514298D0 (en
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Dr Karl Seitz
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Novartis AG
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Ciba Geigy AG
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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
    • 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
    • C09B62/44—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
    • C09B62/02—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
    • C09B62/44—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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

1 GB 2 162 193 A 1
SPECIFICATION
Reactive dyes, process for their preparation and use thereof The present invention relates to reactive dyes and to the use thereof for dyeing or printing textile fibre 5 materials.
Specifically, the present invention relates to reactive dyes of the formula H? VH2 IN Z 1IN\ -NH-A-A I-N = N-1p 11 T-N - N-,-,l B-±NH- Z HY03 S (s6 A) 0. X:1 2 cl 3 0-2 1 'so 3 H 3 0-2 cl (1).
wherein each of Z, andZ2 independently of the other is a radical of the formula -N R, R2 _(2), R, is alkyl which may be substituted by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, carboxy, cyano, chlorine, sulfo or sulfato, and R, is hydrogen, alkyl which may be sub stituted by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbony], alkoxycarbonyl, alkylcarbonyloxy, carboxy, cy ano, chlorine, sulfo or sulfato, or is phenyl, benzyi or phenethyl, the benzene ring of which may be substituted by methyl, methoxy, acetylamino, chlorine, bromine, carboxy or sulfo, and the benzene rings A and B may be further substituted.
The substituent R, is straight chain or branched and preferably contains 1 to 6 carbon atoms. Examples of R, are the following substituent: carboxymethyl, p-carboxyethy], 0- carboxypropy], methoxycarbonyl methyl, ethoxycarbonyl methyl, P- methoxyethyl, P-ethoxyethy], P-meth oxyp ropy[, P-chloroethyl, -v-chloro- 30 propyl, y-bromopropyl, p-hydroxyethyl, y-hydroxypropyl, P-hydroxybutyl, p- cyanoethyl, sulfomethyl, p sulfoethyl and P-sulfatoethyl. If the substituent R, is an alkyl radical, it is straight chain or branched and likewise preferably contains 1 to 6 carbon atoms; R, may be further substituted, as indicated above for formula (2). Exampes of R2 are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbuty], tert-butyl, n pentyl and n-hexyi, as well as the substituents cited above as examples of R,.
As a non-aliphatic substituent, R is preferably the phenyl radical.
Examples of further substituents at the benzene rings A and B are: alkyl groups containing 1 to 4 car bon atoms such as methyl, ethyl, propyl, isopropyl or butyl, alkoxy groups containing 1 to 4 carbon at oms such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, acylamino groups containing 2 to 4 carbon atoms such as acetylamino, propionylamino or butyrylamino, amino, alkylamino containing 1 to 4 40 carbon atoms such as methylamino, ethylamino, propylamino, isopropylamino or butylamino, alkoxycar bonyl containing 1 to 4 carbon atoms in the alkoxy moiety such as methoxycarbonyl or ethoxy- carbony], alkylsulfonyl containing 1 to 4 carbon atoms such as methylsulfonyl or ethyisuifony], trifluoromethy], ni tro, cyano, halogen such as fluorine, chlorine or bromine, carbamoyl, Nalkylcarbamoyl containing 1 to 4 carbon atoms in the alkyl moiety such as N-methylcarbamoyl or Wethylcarbamoyl, sulfamoyl, N- alkyl- 45 sulfamoyl containing 1 to 4 carbon atoms such as N-methyisulfamoyi, Wethyisulfamoyl, N-propyisulfa moyl, Wisopropylsulfamoyl or n- butyisulfamoyi, ureldo, hydroxy, carboxy or sulfomethyl. A and B preferably contain as further substituents methyl, ethyl, methoxy, ethoxy, acetylamino, chlorine, bromine, ureido, hydroxy, carbogy or sulfomethyl.
The reactive dyes of formula (1) contain two removable chlorine atoms which can react in the manner 50 of a nucleophilic substitution and are therefore fibre-reactive.
By fibre-reactive compounds are meant those compounds which are able to react with the hydroxyl groupsof cellulose, with the amino, cdrboxyl, hydroxyl and thio groups of wool and silk, or with.the amino groups and, if present, carboxyl groups of synthetic polyamides to form covalent chemical bonds.
Preferred embodiments of the reactive dyes of formula (1) are:
a) Reactive dyes of formula (1), wherein the coupling component is 1amino-8-hydroxynaphthalene 3,6-diSuifonic acid, and Z, Z,, A and B are as defined for formula (1).
b) Reactive dyes of formula (1), wherein Z, has the same meaning as Z,, and the benzene rings A and B contain no further substituents apart from 0 to 2 sulfo groups.
c). Reactive dyes of formula (1), wherein each of the benzene rings A and B contains a sulfo group. 60 d) Reactive dyes of the formula 2 GB 2 162 193 A 2 z A XII el-N H? VH 2 N- 101 41-N = N- IN\ 1 HO S/:-./ V/ \so H 11so 3 11 3 - 3HO 3 (3) _z 2 X S wherein Z1 and Z, are as defined for formula (2).
e) Reactive dyes of formula (3), wherein Z, and Z, are hydroxy-C,-C4alkylamino, N-C,-C,alkylarnino, lo N-C,-C, alkyi-N-hydroxy-C,-C,, alkylamino, N,N-dihydroxy-C,-Q, alkylamino or N-phenyl-N-hydroxy-C,-C, al10 kylamino.
f) Reactive dyes of the formula z --N = N- N = N- 1-N11- -Z 2 so 3 11 110 3 S / \M V/ \so 3 11 110 3 S V (4), wherein Z, and Z, are as defined in e).
g) Reactive dyes of formula (4), wherein Z, and Z2 are phydroxyethylamino, N,N-di-p-hydroxyethy- 20 [amino, N-methyi-N-p-hydroxyethylamino, N-ethyl-N-P-hydroxyethylamino, tri(hydroxymethyl)methylamino or N-phenyl-N-P-hydroxyethylamino.
Particularly preferred is: h) The reactive dye of the formula F2 HOCH 2 CH 2 NH_ -NH- 11 t-N = N-t 11 1-N = N-e/ NHCH 2 CII 2 OH 0 S03 It H03S /%/%"\ so 3 H HO 3 S (5).
The process for the preparation of reactive dyes of formula (1) comprises coupling and condensing, in suitable sequence, 1-amino8-hydroxynaphthalene-3,6-disuifonic acid or 1- amino-8-hydroxynaphthalene 4,6-disulfonic acid, benzenediazo components (A) and (B), 2,4,6trichloro-s-triazine and amino corn pounds (Z,) andior (Z,).
As the individual process steps referred to above can be carried out in varying sequence and, if de sired, in some cases can be carried out simultaneously different variants of the process are possible. In general, the reaction is carried out stepwise in succession, with the sequence of the simple reactions between the individual reactants conveniently being chosen in accordance with the special conditions. It is known to carry out coupling first in acidic medium in the o-amino position and then in alkaline me- 40 dium in ihe o-hydroxy position since 1-amino-8-naphthoisulfonic acids which are first coupled in alkaline medium (o-hydroxyazo dyes) can not be further coupled to give disazo dyes.
Important process variants comprise:
1) condensing 2 mol of 2,4,6-trichloro-s-triazine with 1 mol of a disazo compound of the formula 45 it 2 NH 2 // k\.
0 ---N N-0 (6) SO- H 110 S \so H 110 S 50 3 3 3 3 and condensing the resultant d[primary condensation product in the molar ratio of 1:2 with an equimolar mixture of amines (Z,) and R2) to give a reactive dye of formula (4); 2) condensing 2 mol of 2,4,6-trichloro-s-triazine with 2 mol of an amine (Z,) or (Z,) and condensing the resultant primary condensation product with 1 mol of a disazo compound of formula (6) to give a 55 reactive dye of formula (4), (Z, Z2); 3) condensing 2 mol of 2,4,6-trichloro-s-triazine with 1 mol of a disazo compound formula (6) and condensing the resultant diprimary condensation product with 2 mol of an amine (Z, or Zj to give a reactive dye of formula (4), (Z, = Zj; 4) condensing 2 mol of 2,4,6-trichloro-s-triazine with 2 mol of 1,3phenylenediamine-4-suifonic acid, 60 condensing the primary condensation product with 2 mol of an amine (Z,) or (Z2), diazotising the result ant secondary condensation product and then effecting coupling, first in strongly acidic solution and then in neutral soluion, with 1-amino-8-hydroxynaphthalene-3,6-disuifonic acid to give a reactive dye of for mula (4), (Z, Z2); 5) condensing 2 mol of 2,4,6-trichloro-s-triazine with 2 mol of 1,3- phenylenediamine-4-suifonic acid, 65 3 GB 2 162 193 A 3 diazotising the primary condensation product and then effecting coupling, first in strongly acidic solution and then in neutral solution, with 1-amino-8- hydroxynaphthalene-3,6- disuifonic acid, and condensing the resultant disazo dye with 2 mol of an amine (Z,) or (Z,) to give a reactive dye of formula (4), (Z, = Zj.
The procedure is the same when using 1-amino-8-hydroxynaphthalene- 4,6disuifonic acid as coupling component or where using other diazo components, e.g. 1,4- phenylenediamine-2-suifonic acid.
The disazo compounds of formula (6) are prepared by coupling 1,8aminonaphthol-3,6-disuifonic acid with 2 equivalents of diazotised 5-nitraniline-2-suifonic acid (acidic and alkaline coupling) and subse quently reducing the nitro groups or by coupling 1,8- aminonaphthol-3,6disuifonic acid with 2 equiva lents of diazotised 5-acetylaminoaniline-2-suifonic acid and subsequently saponifying the acetylamino groups. In practice, the acid coupling is carried out by adding a solution of 1-amino-8-hydroxynaphtha- 10 line-3,6- disulfonic acid to the strongly acidic diazo suspension. The subsequent alkaline coupling is ef fected in known manner in weakly alkaline medium. It is preferred to carry out the coupling of the monoazo"compound with a further equivalent of the diazo components in alkaline bicarbonate solution.
The saponification of the two acetylamino groups after completion of the alkaline coupling is carried out in known manner with alkaline compositions. It is preferred to carry out the saponification with sodium 15 hydroxide.
It is preferred to carry out the condensation of the 2,4,6- trichloro-striazine with the amines (Z,) and/or (Z,) and the disazo compound of formula (6) or the diazo components (A) and (B) in aqueous solution or suspension, at low temperature and at a weakly acidic,-neutral to weakly alkaline pH value. It is advanta geous to neutralise the hydrogen halide set free during the condensation by the continuous addition of 20 aqueous alkali metal hydroxide, carbonate or bicarbonate.
Possible starting materials which can be used for the preparation of reactive dyes of formula (1) are listed individually below:
Coupling components:
1-amino-8-hydroxynaphthalene-3,6-disuifonic acid (H acid), 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid (K acid) Diazo components:
1,3-diaminobenzene, 1,4-diaminobenzene, 1,3-diamino-4-chlorobenzene, 1,3diamino-4-methyl benzene, 30 1,3-dia mino-4-ethyl benzene, 1,3-diamino4-methoxybenzene, 1,3-diamino- 4-ethoxybenzene, 1,4-diarnino 2-methylbenzene, 1,4-diamino-2-methoxybenzene, 1,4-diamino-2- ethoxybenzene, 1,4-diamino-2-chloro benzene, 1,4-dia m i no-2,5-d i methyl benzene, 1,4-diamino-2,5- diethylbenzene, 1,44am i no-2-m ethyl -5-m eth oxybenzene, 1,4-diamino-2,5-dirnethoxybenzene, 1,4-diamino-2,5diethoxybenzene, 1,3-diamino-2,4,6 trimethyl benzene, 1,4A i am! n o-2,3,5,6-tetra methyl - benzene, 1,3- diami no-4-nitro benzene, 1,4-diaminoben- 36 zene-2-sulfonic acid, 1,4-diaminobenzene-2,5-disuifonic acid, 1,4- diaminobenzene- 2,6-disulfonic acid, 1,3 diaminobenzene-4-suifonic acid ' 1,3- diaminobenzene-4,6-disuifonic acid, 1,4-diamino-2-chlorobenzene- 5 suffonic acid, 1,4-diamino-2-methyibenzene-5-suifonic acid, 1,5- diamino6-methyibenzene-3-suifonic acid, 1,3-diamino-6-methyl benzene- 4-sulfonic acid, 1,4-diaminobenzene-2- carboxylic acid, 1,3-diaminobenzene 4-carboxylic acid, 1,2-diaminobenzene-4-carboxylic acid, 1,3diaminobenzene-5-carboxylic acid, 1-amino- 40 4-m ethoxy-5-a m i no methyl benzene- 6-sulfonic acid, 1-amino-3- nitrobenzene-6-suifonic acid or 1amino-4 nitrobenzene-6-suifonic acid.
If an aminoacetylamino compoundls to be used as diazo component instead of a diamine, from which compound the acetyl group is subsequently removed by saponification as explained above in the de scription of the process variants, it may be a monoacetyl compound of one of the diazo components listed above, e.g. 1- amino-4-acetyi-aminobenzene-2-sulfonic acid or 1amino-4-acetylamino- obenzene-3 sulfonic acid, 1-amino-3-acetylaminobenzene-4-suifonic acid or 1-amino-3acetylaminobenzene-6-suifonic acid, 1-amino3-acetylaminobenzene-4,6-disuifonic acid, 1-amino-4acetylaminobenzene-2,5-disuifonic acid or 1'-'amino-4-acetylaminobnzene-2,6-disuifonic acid, 1-amino-3acetylamino-4-methyibenzene-6-sul- fonic acid.
Reactive component: 2,4,6-trichloro-s-triazine (cyanuric chloride).
Amines (Zl) and (Z,):
methoxyethylamine, ethoxyethylamine, methoxypropylamine, chloroethylamine, hydroxyethylamine, dih ydroxyethylamine, hydroxypropylamine, aminoethanesulfonic acid, p- sulfatoethylamine, N-pheny]-N-p hydroxyethylamine, N-methyl-N-P-hydroxyethylamine, Wethyl- N-phydroxyethylamine, tri (hyd roxymethyl) methyl amine.
The reactive dyes of formula (1) are suitable for dyeing and printing a very wide range of materials such as'silk, leather, wool, polyamide fibres and polyurethanes, and especially cellulosic fibre materials of all kinds. Examples of such fibre materials are natural cellulose fibres such as cotton, linen and hemp, as well as cellulose and regenerated cellulose. The reactive dyes of the formula (1) are also suitable for dyeing or printing fibres which contain hydroxyl groups and which are components of blended fabrics, e.g. of blends of cotton with polyester or polyamide fibres.
4 GB 2 162 193 A 4 The dyes of this invention can be applied in different manner to the fibre material and fixed thereon, especially in the form of aqueous dye solutions and printing pastes. The reactive dyes of formula (1) are suitable both for the exhaust process and for dyeing by the pad dyeing process, in which the goods are impregnated with aqueous dye solutions which may also contain salts, and the dyes are fixed after treat- ment with alkali, or in the presence of alkali, with or without the application of heat. The dyes of this invention are also particularly suitable for the so-called cold pad-batch method, which comprises applying the dye together with the alkali on the pad and subsequently fixing the dye by storing the impregnated goods for several hours at room temperature. After fixation the dyeings or prints are thoroughly rinsed with cold and hot water, if necessary with the addition of a compound which acts as a dispersant and promotes the diffusion of non-fixed dye. The reactive dyes of formula (1) are also suitable for print- 10 ing, especially on cotton, and for printing nitrogen-containing fibres, e.g. wool, silk or blends containing wool.
The reactive dyes of formula (1) are particularly suitable for dyeing by the exhaust process; the degrees of fixation are high and non-fixed dye can be readily washed off. - The dyeings and prints obtained with the dyes of this invention on cellulosic fabrics have excellent 15 tinctorial strength and excellent dye-fibre bond stability both in acidic and in alkaline medium, and they also have good light fastness and very good wetfastness properties such as fastness to washing, water, sea-water, cross- dyeing and perspiration, as well as good fastness to pleating, ironing and rubbing.
The invention is illustrated by the following Examples in which parts and percentages are by weight, unless otherwise stated. The ratio of parts by weight to parts by volume is the same as that of kilograms 20 to litres.
The preparation of the monoazo or disazo intermediates is not described in all of the following Examples. However, any undisclosed preparation is clearly evident from what has been stated above.
Example 1: 21.5 parts of the disazo dye of the formula ?H P2 21\ N = N- A' so 3 H HO 3 S SQ 3 H 110 3 S 30 are dissolved in 300 parts of ice water to give a neutral solution towhich is added, with good stirrin'g, a solution of 11.4 parts of cyanuric chloride in 60 parts of acetone. The temperature increases to 15 to 200C, while keeping the pH value at 6 to 7 by the dropwise addition of a solution of 1-n sodium hydroxide.
When acylation of the two terminal amino groups is complete, 4 parts of ethanolamine are added to the 35 dye suspension, the reaction mixture is heated to 40 to 45'C and the pH is kept at 8 by the dropwise addition of a solution of 1-n sodium hydroxide, Amidation is complete after 1 to 2 hours. The dye is precipitated from the resultant solution by adding 10% by volume of sodium chloride, then isolated by filtration and dried in vacuo at 60'C.
The resultant dye of the formula Y1 Y1 - 0 0.
/ \\ ?" P2 IN 0 4 4, 0. 9 Cu Ir.,LI-Cil... 'I-N = N- ---N = N- --',!ICII C11 011 2 2 1 11 1 11 1 \ 1/1 2 2 V1 lio 3 5-9 \ - ---SO3 H A // N so 3 11 110 3 S dyes cotton by the exhaust process in navy blue shades.
Similar dyes are obtained by carrying out the amidation in this Example replacing ethanolamine by the corresponding amount of one of the following amines: 50 Cl, CII Lilt diethanola-aine 11,,, 2 2 \Cli1CH 1011 N-mLthylethanolamine cl, NII-CII CI!,0[1 55 f.7 - - N-cthylethanolar2ine CII C11 -.P.-CH CH 011 - 3 2 2 2 / CP 011 tris(hydroxymetliyl)aminometliane p 2 N-C \ C11 2 011 60 CH 2 011 N-oxethylaniline /-NII-CH 2 CH 2 OH GB 2 162 193 A 5 Example 2: A solution of 44 parts of 1,3-phenylenediamine-4- sulfonic acid in 250 parts by volume of water and 30 parts of a 30% solution of sodium hydroxide are added over about 112 hour to a suspension of 44 parts of cyanuric chloride in 250 parts of ice water. The pH value is subsequently adjusted to 6.5 by slowly adding dropwise a 30% solution of sodium hydroxide. As soon as the diamine is no longer de- tected, % parts of ethanolamine are added to the cold suspension of the monocondensate. The pH value is kept at 9 to 10.5 by the addition of a 30% solution of sodium hydroxide at 10 to 200C. 54 parts by volume of a solution of 4-n sodium nitrite are added to the resultant solution and diazotisation is effected by running the mixture into a vessel containing 54 parts of hydrochloric acid in 150 parts by volume of water. Diazotisation is complete within a few minutes. Any excess nitrite is destroyed with sulfamic acid.
A solution of 31.9 parts of 1-amino-8-naphthol-3,6-disuifonic acid in 150 parts by volume of water and 9 10 parts of a solution of sodium hydroxide is then added to this diazo suspension at 10 to 20'C. Coupling is carried out by the addition of a 30% sodium hydroxide solution or sodium acetate stepwise from pH 2.0 to 3. 5, and the pH is then adjusted to 7.0.
The dye suspension is made up to 1800 parts and the dye is salted out at 600C by the addition of 9% by volume of sodium chloride.
Further valuable reactive dyes which dye cotton in the shades indicated in column 4 of Table 1 are obtained by coupling the diazotised diazo component indicated in column 2 in acid medium to 1- amino8-hydroxynaphthalene-3,6-disuifonic acid, and coupling the diazotised diazo component indicated in column 3 to the monoazo compound so obtained.
TABLE 1
No. Diazo component Diazo component Shade 1 2-(3'-amino-4'-sulfophenylamino)-4- 2-(X-amino-4'- sulfophenylamino)-4navy blue 25 chloro-6-(p-hydroxyethylamino)- chloro-6-(p-suifoethylamino)1,3,5 1,3,5-triazine triazine 2 2-(3'-arnino-4'-sulfophenylamino)-42-3'-amino-4'- sulfophenylamino)-4- navy blue chloro-6-(p-hydroxyethylamino)- chloro-6-(dihydroxyethylamino)- 1,3,51,3,5-triazine triazine 3 2-(3'-amino-4'-suifophenylamino)-42-(3'-amino-4'- sulfophenylamino)-4- navy blue chloro-6-(p-hydroxyethylamino)- chloro-6-(N-phenyl-N-P-hydroxyethy]1,3,5-triazine amino)-1,3,5-triazine 35 4 2-(3'-amino-4'-suifophenylamino)-4- 2-(X amino-4'-suifophenylamino)-4navy blue chloro-6-(p-hydroxyethylamino)- chloro-6-(N-ethyi-N-phydroxyethyl) 1,3,5-triazine amino)-1,3,5-triazine 2-(4'-amino-3'-Sbifophenylamino)-4- 2-(4'-amino-3'-sulfophenylamino)-4greenish chloro-6-(p-hydroxyethylamino)- chloro-6-(p-hydroxyethylamino) 1,3,5- navy blue 1,3,5-triazine triazine 6 2-(4'-amino-3'-suifophenylamino)-4- 2-(4'-amino-3'- sulfophenylamino)-4greenish 45 chloro-6-(p-suifoethylamino)-1,3,5chloro-6-(p-suifoethylamino)-1,3,5- navy blue triazine triazine 7 2-(4'-amino-3'-suifophenylamino-4- 2-(4'-amino-X- sulfophenylamino)-4greenish so chloro-6-(dihydroxyethylamino)chloro-6-(dihydroxyethylamino)-1,3,5- navy blue 50 1,3,5-triazine triazine 8 2-(4'-amino-3'-suifophenylamino)-4- 2-4'-amino-X- sulfophenylamino)-4geenish chforo-6-(ethoxyethylamino)-1,3,5- chloro-6-(ethoxyethylamino)1,3,5- navy blue triazine triazine 55 9 2-(4'-amino-3'-suifophenylamino)-4- 2-(4'-amino-3'-suifophenylamino)-4greenish eh lo ro-6-(N -ethyl - N-p-hyd roxyethyl- chloro-6-(N-ethyi-NP- hydroxyethyl- navy blue amino)-1,3,5-triazine amino)-1,3,5-triazine 60 2-(4'-amino-3'-suifophenylamino)-4- 2-(4'-amino-3'- sulfophenylamino)-4greenish chloro-6-(N-phenyi-N-p-hydroxyethyi- chloro-6-(N-phenylN-p-hydroxyethy]- navy blue amino)-1,3,5-triazine amino)-1,3,5-triazine 6 GB 2 162 193 A 6 11 2-(3'-a m in o-4'-su Ifo p he nyl a mino)-4eh 1 o ro-6-(p-su Ifoethyl am i no) -1,3,5triazine 12 2-(X-a m i no-4'su Ifo phenyl a mi no)-4eh 1 o ro-6-(di hyd roxyethyla mi n o)-1,3,5triazine 13 2-(X-a m i no-4'-su Ifophenyl am i no)-4eh 1 o ro-6-(N-p h enyl -N-P- hyd roxyethylam in o)-1,3,5-tri azin e 14 2-(3'-a m ino-4'-su Ifo ph e nyla mi no)-4eh 1 o ro-6-(N -ethyl-N-p- hydroxyethylam in o)-1,3,5-triazine 2-(3'-amino-4'-suifophenylamino)-4chloro-6-(p-hydroxyethylamino)-1,3, 5triazine 16 2-(3'-amino-4'-suifophenylamino)-4chloro-6-(p-hydroxyethylamino)1,3,5triazine 17 2-(3'-amino-4'-suifophenylamino)-4chloro-6-(p-hydroxyethylamino)1,3,5triazine 18 2-(3'-amino-4'-suifophenylamino)-4chloro-6-(p-hydroxyethylamino)1,3,5triazine 2-(3'-amino-4'-suifophenylamino)-4chloro-6-(p-hydroxyethylamino)1,3,5triazine 2-(3'-amino-4'-suifophenylamino-4chloro-6-(p-hydroxyethylamino)1,3,5triazine 21 2-(4'-amino-2',5'-disuifophenylamino)-4-chloro-6-(p-hydroxyethy]arnino)-1, 3,5-triazine 22 2-(4'-amino-2',5'-disulfophenylamino)-4-chloro-6-(phydroxyethyiarnino)-1,3,5-triazine 2-(3'-amino-4'-suifophenylamino)-4navy blue chloro-6-(p- hydroxyethylamino)-1,3,5triazine 2-(X-a m i no-4'-s u Ifo phenyl a mi no)-4- navy blue 5 chloro-6-(p-hydroxyethylamino)-1,3,5triazine 2-(X-amino-4'- sulfo phenyl a mi no)-4- navy blue chloro-6-(p-hydroxyethyl arnino)-1,3,5 triazine 2-(X-amino-4'suifophenylarnino)-4- navy blue chloro-6-(p-hydroxyethylamino)-1,3,5triazine 2-(4'-amino-X- suifophenylamino)-4- navy blue chloro-6-(p-hydroxyethylamino)-1,3,5- triazine 2-(4'-amino-Xsulfophenylarnino)-4- navy blue chloro-6-(0-suifoethylamino)- 1,3,5 triazine 2-(4'-amino-3'-suifophenylamino)-4- navy blue 25 chloro-6(dihydroxyethylamino)- 1,3,5triazine 2-(4'-amino-X- suifophenylamino)-4navy blue chloro-6-(ethoxyethylamino)- 1,3,5 triazine 2-(4'-amino-3'-suifophenylamino)-4- navy blue chloro-6-(N-ethy]-N-0hydroxyethy]amino)-1,3,5-triazine 2-(4'-amino-2',5'-disuifophenylamino)-4-chloro-6-(p-hydroxyethy]amino)-1, 3,5-triazine 24 2-(4'-amino-2',5'-disulfophenylamino)-4-chloro-6-(phydroxyethy]arnino)-1,3,5-triazine 2-(4'-a m i no-T,5'-cl isu Ifo phenylamino)-4-chloro-6-(p- hydroxyethy]arnino)-1,3,5-triazine 26 2-(3'-amino-4'-suifophenylamino)-4chloro-6-(p-hydroxyethylamino)-1,3, 5triazine 2-(4'-amino-3'-suifophenylamino-4- navy blue chloro-6-(N-phenyl-N-p- hydroxyethy]arnino)-1,3,5-triazine 2-(3'-amino-4'-suifophenylamino)-4- navy blue chloro-6-(phydroxyethylamino)-1,3,5triazine 2-(X-amino-4'- sulfophenylarnino)-4- navy blue 45 chloro-6-(p-sulfoethylamino)-1,3,5- triazine 2-(X-amino-4'sulfophenylarnino)-4- navy blue chloro-6-(dihydroxyethylamino- 1,3,5 triazine 2-(X-amino-4'- sulfophenylarnino)-4- navy blue chloro-6-(N-phenyl-N- p-hydroxyethyl amino)-1,3,5-triazine 2-(X-amino-4'sulfophenylarnino)-4- navy blue chloro-6-(N-phenyi-N-p-hydroxyethyiamino)-1,3,5-triazine 2-(4'-amino-2',5' -disuifophenylamino)- navy blue 4-chioro-6-(p-hydroxyethylamino)-1,3,5- triazine JO 7 27 2-(3'-amino-4'-suifophenylami'no)-4chloro-6-(N-pheny]-N-phydroxyethy]amino)-1,3,5-triazine 28 2-(X-a m in o-4'-su Ifo p h enyl am in o)-4ch 1 o ro-6-(N -ethyl -N -p- hyd roxyethyl am in o)-1,3,5-triazi n e 29 2-(3'-amino-4'-suifophenylamino)-4chloro-6-(p-suifoethylamino)-1,3, 5triazine GB 2 162 193 A 7 2-(4'-a m in o-2',5'-cl isu Ifo p h enyl am in c)- navy blue 4-chloro-6-(p-hydroxyethylamino)-1,3,5- triazine 2-(4'-amino-2',5'-disuifophenylamino)- navy blue 5 4-chloro-6-(phydroxyethylamino)-1,3,5triazine 2-(4'-amino-2'-5'-disuifophenylamino)navy blue 4-chloro-6-(p- hydroxethylamino)-1,3,5triazine Dyeing Procedure 1 2 parts of the dye obtained in Example 1 are dissolved at 20o to 500C in 100 parts of water with the addition of 5 to 20 parts of urea and 2 parts of calcined sodium carbonate. A cotton fabric is impregnated with this solution to a pick-up of 60 to 80% and then dried. The fabric is then thermofixed for 1 112 to 5 minutes at 1400 to 2100C, subsequently soaped for a quarter of an hour in a 0.1% boiling solution of a non-ionic detergent, rinsed and dried.
Dyeing Procedure 2 2 parts of the dye obtained in Example 1 are dissolved at 75'C in 2000 parts of water with the addition of 120 parts of sodium chloride or calcined Glauber's salt. Then 100 parts of a cotton fabric are put into this dyebath and the temperature is kept constant for 30 to 60 minutes. Then 10 parts of calcined sodium carbonate and 4 ml of sodium hydroxide solution (36' 136) are added. The temperature is kept for a fur25 ther 45 to 60 minutes at 750 to 800C and the fabric is then soaped for 15 minutes in a 0.1% boiling solu tion of a non- ionic detergent, rinsed and dried.
Dyeing Procedure 3 2 parts of the dye obtained in Example 1 are dissolved in 100 parts of water while adding 0.5 part of 30 sodium m-nitrobenzenesulfonate. A cbtton fabric is impregnated with this solution to a liquor pick- up of 75% and then dried.
The fabric is then impregnated with a solution of 200C which contains 5 9/1 of sodium hydroxide and 300 g/1 of sodium chloride, and then expressed to a pick-up of 75%. The dyeing is steamed for 30 sec onds at 1000 to 101T, rinsed, soaped for a quarter of an hour in a 0.3% boiling solution of a non-ionic 35 detergent, rinsed and dried.
Dyeing Procedure 4 2 parts of the dye obtained in Example 1 are dissolved in 100 parts of water. The solution is added to 1900 parts of cold water, 60 parts of sodium chloride are added and 100 parts of a cotton fabric are put 40 into this dyebath. The temperature is raised to WC and 40 parts of calcined sodium carbonate and an other 60 parts of sodium.chloride are added after 30 minutes. The temperature is kept for 30 minutes at WC. The dyeing is rinsed and then soaped for 15 minutes in a 0.3% boiling solution of a non-ionic deter gent, rinsed and dried.
Printing Procedure 2 parts of the dye obtained according to Example 1 are sprinkled, with rapid stirring, into 100 parts of a stock thickening which contains 45 parts of 5% sodium alginate thickening, 32 parts of water, 20 parts or urea, 1 part of sodium m-nitrobenzenesulfonate and 2 parts of sodium carbonate. 50 A cotton fabric is printed with the printing paste so obtained on a roller printing machine. The printed 50 fabric is steamed 4 to 8 minutes at 1000C in saturated steam, then thoroughly rinsed in cold and hot water, in the process of which chemically nonfixed dye can be very easily removed from the fabric, and then dried.

Claims (12)

1. A reactive dye of the formula 17.9 tP12 0 \, / "\, / 0 'N t-N = N-1 is, 41 -N = N- I, 7 \ H, 1 z 1 B - z 2 0 S SO H 3 11 \_ - (s6 il) v 11 0-2 50 3 11 3 0-2 - cl C, 1 8 GB 2 162 193 A wherein each of Z, and Z, independently of the other is a radical of the formula 8 R, -N '- R, (2), 5 R, is alkyl which may be substituted by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, carboxy, cyano, chlorine, sulfo or sulfato, and R, is hydrogen, alkyl which may be substituted by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbony], alkoxycarbony], alkylcarbonyloxy, carboxy, cy- ano, chlorine, sulfo or sulfato, or is phenyl, benzy] or phenethy], the benzene ring of which may be. substituted by methyl, methoxy, acetylamino, chlorine, bromine, carboxy or sulfo, and the benzene rings A and B may be further substituted.
2. A reactive dye according to claim 1, wherein the coupling component is 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, and Z,, Z,, A and B are as defined in claim 1.
3. A reactive dye according to claim 2, wherein Z, has the same meaning as z,, and the benzene rings 15 A and B contain no further substituents apart from 0 to 2 sulfo groups.
4. A reactive dye according to claim 3, wherein each of the benzene rings A and B contains a sulfo group.
5. A reactive dye according to claim 1, of the formula c - N-ri 5, 1 0 1 , \ so 3 H 1 wherein Z, and Z, are as defined for formula (2).
H? N11 1 2 v \\. & \\.,.N\ -t = N-1 _Z 7 S so H. - /x,p 3 3 110S (3), \ 2 1
6. A reactive dye according to claim 5, wherein Z, and Z2 are hydroxy-C,- C, aikylamino, WC,-C, alkyl- 30 Whydroxy- C,-C., alkylamino, N, N-dihydroxy-C,-C,a 1 kyl amino or N- phenyl-N-hydroxy-C,-C, alkylamino.
7. A reactive dye according to claim 6, of the formula I r2 1IN\ /. \\ \ /. \\ 0 \\ M- Z ---N = N-, I, ---N = N-loll 1 -IN _Z 2 cl so 3 H HO 3 S so 3 H HO 3 S - (4), 40 wherein Z, and Z, are as defined for claim 6.
8. A reactive dye according to claim 7, wherein Z, and Z, are phydroxyethyl amino, N,N-di-p-hydroxyethylamino, N-methyl-N- phydroxyethylamino, N-ethyl-N-P-hydroxyethylamino, tri(hydroxymethyl)methylarnino or N-phenyl-N-P-hydroxyethylamino.
9 A reactive dye according to claim 8, of the formula Hy TI 2 A HOCH 2 CH 2 NH_ SO. H
10 S so it Ito S j 3 3 3 (5).
= N- / A --1li1CH 2 CII 2 011 10. A process for the preparation of a reactive dye according to claim 1, which process comprises coupling and condensing, in suitable sequence, 1-amino-8hydroxynaphthalene-3,6-disuifonic acid or 1 amino-8-hydroxynaphthalene-4,6-disulfonic acid, benzenediazo components (A) and (B), 2,4,6-trichloro-s- 55 triazine, and amino compounds (Zl) andfor (Z,).
11. A process for dyeing or printing textile fibre material, which comprises the use of a reactive dye according to claim 1.
12. A process according to claim 11 for dyeing cellulosic fibres, especially cotton.
Printed in the UK for HMSO, D8818935, 12185, 7102.
Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.
GB08514298A 1984-07-03 1985-06-06 Reactive dyes, process for their preparation and use thereof Expired GB2162193B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095101A (en) * 1983-12-10 1992-03-10 Sandoz Ltd. 1-Amino-2,7-di-[5'-(2"-chloro-4"-substituted amino-1,3,5-triazin-6"-ylamino)-2'-sulfophenylazo]-3,6-disulfonic acids
US5188640A (en) * 1983-12-10 1993-02-23 Sandoz Ltd. Use of 1-amino-2,7-di-[5'-((2"-chloro-4"-substituted amino-1,3,5-triazin-6-ylamino)-2'-sulfophenylazo]-8-hydroxynaphthalene-3,6-disulfonic acids for dyeing and printing
WO1999025772A1 (en) * 1997-11-17 1999-05-27 Basf Aktiengesellschaft Reactive disazo dyes

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Publication number Priority date Publication date Assignee Title
DE3443962A1 (en) * 1983-12-10 1985-06-20 Sandoz-Patent-GmbH, 7850 Lörrach Reactive disazo compounds
DE3923483A1 (en) * 1989-07-15 1991-01-24 Sandoz Ag FIBER REACTIVE DISOROUS POWERS
GB0411589D0 (en) * 2004-05-24 2004-06-23 Dystar Textilfarben Gmbh & Co Mixtures of fibre reactive azo dyes

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GB1189312A (en) * 1966-08-01 1970-04-22 Ici Ltd Water-Soluble Polyazo Dyestuffs of the Triazine Series
GB1542773A (en) * 1976-08-31 1979-03-28 Ciba Geigy Ag Fibre-reactive fluorotriazine disazo dyes
GB1566921A (en) * 1976-10-20 1980-05-08 Bayer Ag Reactive dyestuffs
EP0120807A1 (en) * 1983-02-24 1984-10-03 Ciba-Geigy Ag Reactive dyes, their preparation and their use
EP0122423A1 (en) * 1983-03-15 1984-10-24 Bayer Ag Disazo reactive dyestuffs, process for their preparation and their use in the dyeing or printing of substrates

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FR1543282A (en) * 1966-08-01 1968-10-25 Ici Ltd Water soluble azo dyes and method of manufacture
JPS5725359A (en) * 1980-06-20 1982-02-10 Ciba Geigy Ag Manufacture of disazo dye

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Publication number Priority date Publication date Assignee Title
GB1189312A (en) * 1966-08-01 1970-04-22 Ici Ltd Water-Soluble Polyazo Dyestuffs of the Triazine Series
GB1542773A (en) * 1976-08-31 1979-03-28 Ciba Geigy Ag Fibre-reactive fluorotriazine disazo dyes
GB1566921A (en) * 1976-10-20 1980-05-08 Bayer Ag Reactive dyestuffs
EP0120807A1 (en) * 1983-02-24 1984-10-03 Ciba-Geigy Ag Reactive dyes, their preparation and their use
EP0122423A1 (en) * 1983-03-15 1984-10-24 Bayer Ag Disazo reactive dyestuffs, process for their preparation and their use in the dyeing or printing of substrates

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095101A (en) * 1983-12-10 1992-03-10 Sandoz Ltd. 1-Amino-2,7-di-[5'-(2"-chloro-4"-substituted amino-1,3,5-triazin-6"-ylamino)-2'-sulfophenylazo]-3,6-disulfonic acids
US5188640A (en) * 1983-12-10 1993-02-23 Sandoz Ltd. Use of 1-amino-2,7-di-[5'-((2"-chloro-4"-substituted amino-1,3,5-triazin-6-ylamino)-2'-sulfophenylazo]-8-hydroxynaphthalene-3,6-disulfonic acids for dyeing and printing
WO1999025772A1 (en) * 1997-11-17 1999-05-27 Basf Aktiengesellschaft Reactive disazo dyes

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PT80739A (en) 1985-10-01
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CA1243308A (en) 1988-10-18
DK239985D0 (en) 1985-05-29
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ES8703917A1 (en) 1987-03-01
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