CA1243308A - Reactive dyes, process for their preparation and use thereof - Google Patents

Reactive dyes, process for their preparation and use thereof

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Publication number
CA1243308A
CA1243308A CA000483299A CA483299A CA1243308A CA 1243308 A CA1243308 A CA 1243308A CA 000483299 A CA000483299 A CA 000483299A CA 483299 A CA483299 A CA 483299A CA 1243308 A CA1243308 A CA 1243308A
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formula
parts
amino
hydroxy
reactive dyes
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CA000483299A
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French (fr)
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Karl Seitz
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BASF Schweiz AG
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Individual
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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)

Abstract

Reactive dyes, process for their preparation and use thereof Abstract of the Disclosure The invention relates to reactive dyes of the formula (1), wherein each of Z1 and Z2 independently of the other is a radical of the formula (2), R1 is alkyl which may be substituted by hydroxy, alkoxy, hydroxyalkoxy,alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, carboxy, cyano, chlorine, sulfo or sulfato, and R2 is hydrogen, alkyl which may be substituted by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxy-carbonyl, alkylcarbonyloxy, carboxy, cyano, chlorine, sulfo or sulfato, or is phenyl, benzyl 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.

These dyes are particularly suitable for dyeing or printing cellulosic fibre material and give dyeings and prints of good fastness properties.

Description

3~

Case 1-1499~

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 materials.

Specifically, the present invention relates to reactive dyes of the formula ~ ~ 2 ~ N = N -o~;f ~1 - N = N ~ o ~ \~ z 3H~o32 ~`so ~1 (s~3xH)o-2 Cl 3 Cl wherein each of Zl and Z2 independently of the other is a radical of the formula 1 (2), Rl is alkyl which may be substituted by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxycarbonylz alkylcarbonyloxy, carboxy, cyano, chlorine, sulfo or sulfato, and R2 is hydrogen, alkyl which may be substituted by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxy-carbonyl, alkylcarbonyloxy, carboxy, cyano, chlorine, sulfo or sulfato, or is phenyl, benzyl or phenethyl, the benzene ring of which may be substituted by methyl, methoxy, acetylamino, chlorine, bromine, carboxy or sulfo, and the benzene rings ~ and B may be further substituted.

The substituent Rl is straight chain or branched and preferably contains 1 to 6 carbon atoms. Examples of Rl are the Eollowing , '`~1,;, 1 ` ~

3~

substituents: carboxymethyl, ~-carboxyethyl, ~-carboxypropyl, methoxy-carbonylmethyl, ethoxycarbonylmethyl, ~-methoxyethyl, ~-ethoxyethyl, ~-methoxypropyl, ~-chloroethyl, y-chloropropyl, y-bromopropyl, j~-hydroxyethyl, y-hydroxypropyl, ~-hydroxybutyl, ~-cyanoethyl~ sulfo-methyl, ~-sulfoethyl and j~-sulfatoethyl. If the substituent R2 is an alkyl radical, it is straight chain or branched and likewise preferably contains 1 to 6 carbon atoms; R2 may be further substituted, as indicated above for formula (2). Examples of R2 are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl, as well as the substituents cited above as examples of Rl.

As a non-aliphatic substituent, R2 is preferably the phenyl radical.

Examples of further substituents at the benzene rings A and B are~
alkyl groups containing 1 to 4 carbon atoms such as methyl, ethyll propyl, isopropyl or butyl, alkoxy groups containing 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, acyl-amino groups containing 2 to 4 carbon atoms such as acetylamino, propionylamino or butyrylamino, amino, alkylamino containing 1 to 4 carbon atoms such as methylamino, ethylamino, propylamino~ isopropyl-amino or butylamino, alkoxycarbonyl containing 1 to 4 carbon atoms in the alkoxy moiety such as methoxycarbonyl or ethoxycarbonyl, alkyl-sulfonyl containing 1 to 4 carbon atoms such as methylsulfonyl or ethylsulfonyl, trifluoromethyl, nitro, cyano, halogen such as fluorine, chlorine or bromine, carbamoyl, N-alkylcarbamoyl containing 1 to ~i carbon atoms in the alkyl moiety such as N-methylcarbamoyl or N-ethylcarbamoyl, sulfamoyl, N-alkylsulfamoyl containing 1 to 4 carbon atoms such as N-methylsulfamoyl, N-ethylsul~amoyl, N-propylsulfamoyl~
N-isopropylsulfamoyl or n butylsulfamoyl, ureido, hydroxy, carboxy or sulfomethyl. A and B preEerably contain as further substituents methyl, ethyl, methoxy, ethoxy, acetylamino, chlorine, bromine, ureido, hydroxy, carboxy or sulfomethyl.

The reactive dyes of formula (1) contain two removable chlorine atoms which can react in the manner 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 groups oE cellulose, with the amino, carbo-xyl, 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 l-amino-8-hydroxynaphthalene-3,6-disulfonic acid, and Zl' Z2' A and B are as defined for formula (1).
b) Reactive dyes of formula (1), wherein Zl has the same meaning as Z2' and the benzene rings A and B contain no further substituents apart from O to 2 sulfo groups.
c) Reactive dyes of formula (1), wherein each of the benzene rings A
and B contains a sulfo group.

d) Reactive dyes of the formula Z -~ ~ -NH ~ N = N ~ N ~ N
~ ~ S03H 3 3 ~03S

wherein Zl and Z2 are as defined for formula (2).
e) Reactive dyes of formula (3), wherein Zl and Z2 are hydroxy-Cl-C4-alkylamino, N-Cl-C~alkyl-N-hydroxy-Cl-C4alkylamino, N,N-dihydroxy-Cl-C4alkylamino or N-phenyl-N-ilydroxy-Cl-C~alkylamino.

~33~3~

f) Reactive dyes of the formula ~ ~ 2 Z~ -NH~ N = N ~ N = N - It ~-NH~ -Z2 ~1 \o~ \SO H HO 5/ ~o/ \o~ \SO H HO S/ \
(4) , wherein Zl and Z2 are as defined in e).
g) Reactive dyes of formula (4), wherein Zl and Z2 are ~-hydroxyethyl-amino, N,N-di-~-hydroxyethylamino9 N-methyl-N-~-hydroxyethylamino, N-ethyl-N-~-hydroxyethylamino, tri(hydroxymethyl)methylamino or N-phenyl-N-~-hydroxyethylamino.

Particularly prefered is:
h) The reactive dye of the formula . H~ ~H2 HOCH2C~2h~- ~ ~-NH~ t - N = N - ~ N = N ~ I-NH- ~ ~ -NHCH2C~20H
\S~H HO S/ ~4/ \~ \SO ~ ~10 S/ \
(S) The process for the preparation of reactive dyes of formula ~1) comprises coupling and condensing, in suitable sequence, l-amino-8-hydroxynaphthalene-3,6-disulfonic acid or 1-amino-8-hydroxynaphthalene-~,6-disulfonic acid, benzenediazo components (A) and (B), 2,~,6-tri-chloro-s-triazine and amino compounds (Zl) and/or (Z2) As the individual process steps referred to above can be carried out in varying sequence and, if desired, in some cases can be cflrried out simultaneously, different variants of the process are possible. In general, the reaction is carried out stepwise in succession, with the ~2~33~3~

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 medium in the o-hydroxy position since l-amino-8-naphtholSulfonic 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 H2N\ ~ I ~ 2 ~ 2 ~ N = ~ - a~ N = N ~ o \SO H HO S/ ~ \SO H HO S/

and condensing the resultant diprimary condensation product in the molar ratio of 1:2 with an equimolar mixture of amines (Zl) and (Z2) 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 (Zl) or (Z2) and condensing the resultant primary condensation product with 1 mol of a disazo compound of formula (6) to give a reactive dye of formula (4)~ (Zl = Z2);
3) condensing 2 mol of 2,4,6-trichloro-s-triazine with 1 mol of a disazo compound oE formula (6) and condensing the resultant diprimary condensation procluct with 2 mol of an amine (Zl) or (Z2) to give a reactive dye of formula (4)~ (Zl a Z2);
4) condensing 2 mol of 2,4,6-trichloro-s-triazine with 2 mol of 1,3-phenylenediamine-4-sulfonic acid, condensing the primary conden-sation product with 2 mol of an amine (Zl) or (Z2)' diazotising the 3~3 resultant secondary condensation product and then effecting coupling, first in strongly acidic solution and then in neutral solution~ with l-amino-8-hydroxynaphthalene-3,6-disulfonic acid to give a reactive dye of formula (4) 9 (Zl = Z2);

S) condensing 2 mol of 2,4,6-trichloro-s-triazine with 2 mol of 1,3-phenylenediamine-4-sulfonic acid, diazotising the primary conden-sation product and then effecting coupling, first in strongly acidic solution and then in neutral solution, with l-amino-8-hydroxynaphtha-lene-3,6-disulfonic acid, and condensing the resultant disazo dye with 2 mol of an amine (Zl) or (Z2) to give a reactive dye of formula (4), (Zl Z2) The procedure is the same when using l-amino-8-hydroxynaphthalene-4,6-disulfonic acid as coupling component or where using other diazo components, e.g. 1,4-phenylenediamine-2-sulfonic acid.

The disazo compounds of formula (6) are prepared by coupling 1,8-amino-naphthol-3,6-disulfonic acid with 2 equivalents of diazotised
5-nitraniline-2-sulfonic acid (acidic and alkaline coupling) and sub sequently reducing the nitro groups or by coupling 1,8-amino-naphthol-3,6-disulfonic acid with 2 equivalents of diazotised S-acetyl-aminoaniline-2-sulfonic acid and subsequently sapOnifying the acetyl-amino groups. In practice,the acid coupling is carried out by adding a solution of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid to the strongly acidic diazo suspension. The subsequent alkaline COUp-ling is effected 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 a~ter completion of the alkaline coupling is carried out in known manner with alkaline compositions. It is preferred to carry out the saponification with sodium ilydroxide.

3~

It is preferred to carry out the condensation of the 2,4,6-trichloro-s-triazine with the amines (Z]) and/or (Z2) 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 advantageous to neutralise the hydrogen halide set free during the condensation by the continuous addition of aqueous alkali metal hydroxide, carbonate or bicarbonate.

Possible starting materials which can be used for the preparation of reactive dyes of form~lla (1) are listed individually below:

Coupling components:
. . _ . , _ l-amino-8-hydroxynaphthalene-376-disulfonic acid (H acid), l-amino-8-hydroxynaphthalene-4,6-disulfonic acid (K acid).

Diazo components _ _ 1,3-diaminobenzene 9 1,4-diaminobenzene, 1,3-diamino-4-chlorobenzene, 1,3-diamino-4-methylbenzene, 1,3-diamino-4-ethylbenzene9 1,3-diamino-4-methoxybenzene, 1,3-diamino-4-ethoxybenzene, 1,4-diamino-2-methyl-benzene, 1,4-diamino-2-methoxybenzene, 1,4-diamino-2-ethoxybenzene, 1,4-diarnino-2-chlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,5-diethylbenzene, 1,4-diamino-2-methyl-5-methoxybenzene, 1,4-diamino-2,5-dimethoxybenzene, 1,4-diamino-2,5-diethoxybenzene~
1,3-diamino-2,4,6-trimethylbenzene, 1,4-diamino-2,3,5,6-tetramethyl-benzene, 1,3-diamino-4-nitrobenzene, 1,4-diaminobenzene-2-sulfon;c acid, 1,4-diaminobenzene-2,5-disulfonic acid, 1,4-diaminobenzene-2,6-di-sulfonic acid, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonic acid, 1,4-diamino-2-chlorobenzene-S-sulfonic acid, 1,4-diamino-2-methylbenzene-5-sulfon;c acid, 1,5-diamino-6-methyl-benzene-3-sulfonic acid, 1,3-diamino-6-methylbenzene-4-sulfonic acid, 1,4-diaminobenzene-2-carboxylic acid, 1,3-diaminobenzene-4-carboxylic acid, 1,2-diaminobenzene-4-carboxylic acid, 1,3-diaminobenzene-5-~33~3 carboxylic acid, l-amino-4-methoxy-5-aminomethylbenzene-6-sulfonic acid, l-amino-3-nitrobenzene-6-sulfonic acid or 1-amino-4-nitrobenzene-
6-sulfonic acid.

If an aminoacetylamino compound is to be used as diazo component instead of a diamine, from which compound the acetyl group is subse-quently removed by saponification as explained above in the description of the process variants, it may be a monoacetyl compound of one of the diazo components listed above, e.g. l-amino-4-acetyl~
aminobenzene-2-sulfonic acid or 1-amino-4-acetylaminobenzene-3-sulfonic acid, l-amino-3-acetylaminobenzene-4-sulfonic acid or l-amino-3-acetylaminobenzene-6-sulfonic acid, 1-amino-3-acetylamino-benzene-4,6-disulfonic acid, 1-amino-4-acetylaminobenzene-2,5-disulfonic acid or l-amino-4-acetylaminobenzene-2,6-disulfonic acid, l-amino-3-acetylamino-4-methylbenzene-6-sulfonic acid.

Reactive component:
2,4,6-trichloro-s-triazine (cyanuric chloride)~

Amines (Zl) and (~2) methoxyethylamine, ethoxyethylamine, methoxypropylamine, chloroethyl-amine, hydroxyethylamine, dihydroxyethylamine, hydroxypropylamine, aminoethanesulfonic acid, ~-sulfatoethylamine, N-phenyl-N-~-hydroxy-ethylamine, N-methyl-N-~-hydroxyethylamine, N-ethyl-N-~-hydroxyethyl-amine, tri(hydroxymethyl)methylamine.

The reactive dyes of formula (1) are suitable Eor dyeing and printing a very wide range oE materials such as silk, leather, wool, polyamide Eibres and polyurethanes, and especially cellulosic Eibre materials of all kinds. ~xamples oE 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 ':

~3~

and which are components of blended fabrics, e.g. of blends of cotton with polyester or polyamide fibres.

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 treatment with alkali, or in the presence of alkali, with or without the application of heat. The dyes of this invention are also particu-larly suitable for the so-called cold pad-batch method, which com-prises applying the dye together with the alkali on the pad and sub-sequently 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 printing, 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 tinctorial strength and excellent dye-fibre bond stability both in aciclic 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.

~33~3 The invention is lllustrated 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 to litres, The preparation of the monoazo or disazo intermediates is not describedin 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 IOH ~H2 2 ~ = N ~ N = N - ~/ ~t~ 2 ;o~ ;SO H HO S/ ~-/ \o~ ;SO H HO S/ \ ~

are dissolved in 300 parts of ice water to give a neutral solution to which is added, with good stirring, a solution of 11.4 parts o~
cyanuric chlor;de in 60 parts of acetone. The temperature increases to 15 to 20~C, while keeping the pH value at 6 to 7 by the dropwise addition of a solution of l-n sodium hydroxide. When acylation of the two terminal amino groups is complete, 4 parts of ethanolamine are added to the dye suspension, the reaction mixture is heated to 40 to 45C and the pH is kept at 8 by the dropwise addition of a solution of l-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 60C.
The resultant dye of the formula i,Cl ~1 2 2 \ ~ 11 i HO S i 11 i so H 11 1 \;~ Z 2 33~9 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:

diethanolamine HN

N-methylethanolamine CH3-NH-CH2CH20H
N-ethylethanolamine CH3CH2-NH-CH2CH20H
~CH20H
tris(hydroxymethyl)aminomethane _ .
N-oxethylaniline \ /'-NH-CH2CH20H .
=.

Example 2: A solution of 44 parts of 193-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 1/2 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 detected, 16 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 20C. 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 l-amino-8-naphthol-396-disulfonic acid in 150 parts by volume of water and 9 parts of a solution of sodium 3~

hydroxide is then added to this diazo suspension at 10 to 20C.
Coupling is carried out by the addition of a 30% sodium hydroxide solution or sodi~lm acetate stepwise from pH 2.0 to 3.5, and the pH is then adjusted to 7Ø
The dye suspension is made up to 1800 parts and the dye is salted out at 60C by the addition of 9 ~ by volume of sodium chloride.

Further valuable reactive dyes which dye cotton in the shades indicatedin column 4 of Table 1 are obtained by coupling the diazotised diazo component indicated in column 2 in acid medium to 1-amino-8-hydroxy naphthalene-3,6-disulfonic acid, and coupling the diazotised diazo component indicated in column 3 to the monoazo compound so obtained.

- 13 - ~33~

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o ~ X
~ X r~l ~ l 1.1 _ O _ O
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u~ ~ .,1 u~ o ~ I o W ~ O I ~ _I ~ p ~
~ b~ ~ .a cz~ az~
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, ~ I b r~ I b^ I ~ ^ I ~ rl a --~ N _S ~ o ~ ~ o w I W ~ EWi I ~3 EW~ V
_ . . - 'I
zo ~ C`l C`l C`J C~l C~

~3~

Dyeing Procedure 1 2 parts of the dye obtained in Example 1 are dissolved at 20 to 50C
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 1/2 to 5 minutes at 140 to 210C, 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 75C 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 Bé) are added. The temperature is kept for a further 45 to 60 minutes at 75 to 80C and the fabric is then soaped for 15 minutes in a 0.1 % boiling solution 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 sodium m-nitrobenzenesulfonate..
A cotton 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 20C which contains 5 g/l of sodium hydroxide and 300 g/l of sodium chloride, and then expresse~ to a pick-up of 75 %. The dyeing is steamed for 30 seconds at 100 to 101C, rinsed, soaped for a quarter of an hour in a 0.3 % boiling solution of a non-ionic detergent, rinsed and dried.

~ lo -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 into this dyebath. The temperature is raised to 60C and 40 parts of calcined sodium carbonate and another 60 parts of sodium chloride are added after 30 minutes. The temperature is kept for 30 minutes at 60C. The dyeing is rinsed and then soaped for 15 minutes in a 0.3 % boiling solution of a non-ionic detergent, 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.

A cotton fabric is printed with the printing paste so obtained on a roller printing machine. The printed fabric is steamed 4 to 8 mimltes at 100C 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 (8)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A reactive dye of the formula (3) (3), wherein Z1 and Z2 are hydroxy-C1-C4alkylamino, N-C1-C4alkyl-N-hydroxy-C1-C4alkylamino, N, N-dihydroxy-C1-C4alkylamino or N-phenyl -N-hydroxy-Cl-C4alkylamino.
2. A reactive dye according to claim 1, of the formula (4) wherein Z1 and Z2 are as defined in claim 1.
3. A reactive dye according to claim 2, wherein Z1 and Z2 are .beta.-hydroxyethylamino, N, N-di-.beta.-hydroxyethylamino, N-methyl-N-.beta.-hydroxyethylamino, N-ethyl-N-.beta.-hydroxyethylamino, tri(hydroxy-methyl)-methylamino or N-phenyl-N-.beta.-hydroxyethylamino.
4. A reactive dye according to claim 3, of the formula (5) (5).
5. A process for the preparation of a reactive dye accord-ing to claim 1, which process comprises coupling and condensing in suitable sequence, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, benzenediazo components corresponding to rings (A) and (B), 2, 4, 6 trichloro-s-triazine, and amino compounds (Z1) and/or (Z2).
6. A process for dyeing or printing textile fibre material which comprises applying thereto a reactive dye according to claim 1.
7. A process according to claim 6, wherein the textile fibre material comprises cellulosic fibres.
8. A process according to claim 7 wherein the textile fibre material is cotton.
CA000483299A 1984-07-03 1985-06-06 Reactive dyes, process for their preparation and use thereof Expired CA1243308A (en)

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CH320184 1984-07-03

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Publication number Priority date Publication date Assignee Title
FR2556358B1 (en) * 1983-12-10 1987-01-02 Sandoz Sa NOVEL BISAZOIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS DYES
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
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
GB9724288D0 (en) * 1997-11-17 1998-01-14 Basf Ag Reactive disazo dyes
GB0411589D0 (en) * 2004-05-24 2004-06-23 Dystar Textilfarben Gmbh & Co Mixtures of fibre reactive azo dyes

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FR1543282A (en) * 1966-08-01 1968-10-25 Ici Ltd Water soluble azo dyes and method of manufacture
GB1189312A (en) * 1966-08-01 1970-04-22 Ici Ltd Water-Soluble Polyazo Dyestuffs of the Triazine Series
LU75689A1 (en) * 1976-08-31 1978-04-13
DE2647312A1 (en) * 1976-10-20 1978-04-27 Bayer Ag REACTIVE COLORS
JPS5725359A (en) * 1980-06-20 1982-02-10 Ciba Geigy Ag Manufacture of disazo dye
DE3476218D1 (en) * 1983-02-24 1989-02-23 Ciba Geigy Ag Reactive dyes, their preparation and their use
DE3325788A1 (en) * 1983-03-15 1984-09-20 Bayer Ag, 5090 Leverkusen FIBER REACTIVE DISAZO DYES, METHOD FOR THEIR PRODUCTION AND THEIR USE FOR COLORING OR PRINTING STUBSTRATES

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GB2162193B (en) 1988-11-02
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PT80739B (en) 1987-10-20
DK239985D0 (en) 1985-05-29
GR851373B (en) 1985-11-25
EP0170612B1 (en) 1989-05-24
ES543896A0 (en) 1987-03-01
IL75471A0 (en) 1985-10-31
AR242420A1 (en) 1993-03-31
JPS6121164A (en) 1986-01-29
JPH0246621B2 (en) 1990-10-16
PT80739A (en) 1985-10-01
GB8514298D0 (en) 1985-07-10
EP0170612A1 (en) 1986-02-05
KR930009899B1 (en) 1993-10-13
ES8703917A1 (en) 1987-03-01
GB2162193A (en) 1986-01-29
DK239985A (en) 1986-01-04
TR23052A (en) 1989-02-14
IE851409L (en) 1986-01-03
AU4444685A (en) 1986-01-09
BR8502804A (en) 1986-05-27
ATE43356T1 (en) 1989-06-15
ZA854248B (en) 1986-02-26
IE57997B1 (en) 1993-06-02

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