IE851409L - Reactive dyes - Google Patents
Reactive dyesInfo
- Publication number
- IE851409L IE851409L IE851409A IE140985A IE851409L IE 851409 L IE851409 L IE 851409L IE 851409 A IE851409 A IE 851409A IE 140985 A IE140985 A IE 140985A IE 851409 L IE851409 L IE 851409L
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- hydroxy
- reactive dye
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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
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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
- C09B62/44—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
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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
- C09B62/02—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
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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
- C09B62/44—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
Novel dyes of formula (1) give dyeings and prints of good fastness on cellulosic, polyamide and polyurethane fibres, silk, leather and wool. <IMAGE> wherein each of Z1 and Z2 independently of the other is a radical of the formula <IMAGE> R1 is alkyl which may be substituted by hydroxy, alkoxy, hydroalkoxy, alkylcarbonyl, alkoxycarbonyl, carboxy, cyano, chlorine, sulfo or sulfato, and R2 is hydrogen, alkyl which may be substituted by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxycarbonyl, 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.
[EP0170612A1]
Description
i> '~S i* i> < f„._ wp PATENTS ACT, 1964 COMPLETE SPECIFICATION REACTIVE DYES, PROCESS FOR THEIR PREPARATION AND USE THEREOF CIBA-GEIGY AG, a body corporate organised according to the laws of Switzerland, of Klybeckstrasse 141, 4002 Basle, Switzerland.
The present invention relates to reactive ayes and to the use thereof for dyeing or printing textile fibre materials.
Specifically, the present invention relates to reactive dyes of the f omul a A r\ • »• C-NH—A I •—N = N—• • N—R I I II I H? F2 A A 2 1 2 CI CI (1) , wherein each of 2^ and Z^ independently of the other is a radical of the formula (2), is alkyl which may be substituted by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, carboxy, cyano, by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, carboxy, cyano, chlorine or sulfate, 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; provided that when is phenyl, then is alkyl which is substituted by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, carboxy, cyano, chlorine or sulfato; and further provided that the compounds of formula I are excluded wherein Zj and are identical radicals selected from 3~hydroxyethy 1-, g-hydroxypropy1-, Y -hydroxypropyl-, -dihydroxypropyl-, £<-hydroxymethyl-p-hydroxy)-ethyl-, yj-metho;cyethyl-, Jf-methoxypropyl-, -ethoxypropyl-, f> -(y5'-hydroxyethoxy)ethyl-, y -(£'-hydroxyethoxy)propyl-, N,N-di-£-hydroxyethyl-, N-^-hydroxyethyl-N-^-hydroxypropyl- , N-j3-cyano- ethyl-N-^-GS'hydroxyethoxy)ethyl- » N-ethyl-N-(/>-hydro:cypropyl)-, N-methyl-N-( As^f-dihyttroxypropyl)- and N-n-propyl-N(^>,$ -dihydroxypropyl )amino.
The substituent Rj is straight chain or branched and preferably contains I to 6 carbon atoms. Examples of Rj are the following chlorine or sulfate, and R^ is hydrogen, alkyl which nay be substituted substituents: carboxvmethyl, p-carboxyethyl, p-carboxypropyl, methoxy-carbonyimethvl, ethoxvearbonylmethyl, P-methoxvethyl, p-ethoxvethyl, |3-mcthoxvpropyl, p-chloroethy1, y-chloropropvl, p-hydrexyethyl, y-hvdro>:ypropyl, p-hydroxvbutvl, p-cyanoethyl, and fi-sulfatoethyl. If the substituent R£ is an alkyl radical, it is straight chain or branched and likewise preferably contains 1 to 6 carbon atoms; may be further substituted, as indicated above for formula (2). Examples of R£ 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 .
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 carbon atoms such as methyl, ethyl, propyl, isopropyl or butyl, alkoxy groups containing 1 to A 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 methylaaino, 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 4 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-methy1sulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl or n-butylsulfamoyl, ureido, hydroxy, carboxy or sulfomethyl. A and B preferably 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 nuclcophilic substitution and are therefore fibre-reactive.
By fibre-rcactive compounds arc meant those compounds which are able to react with the hydroxyl groups of cellulose, with the amino, carbo-xyl, hydroxyl and thio groups of wool and silk, or vith 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 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. d) Reactive dyes of the formula 1 f2 A .'\_„. N—A.A A. ji vf fi I! 1 'i WV"! V X-\o3„ ho/ V V \O3H „ // U (3) . " wherein and Z^ are as defined for formula (•). e) Reactive dyes of formula (3), wherein and Z^ are hydroxy-C^-C^-alkylamino, N-C^-C^alkyl-N-hydroxy-C^-C^alkylamino, N,N-dihvdroxy-C^-C^alkylamino or N-phenyl-N-hydroxy-C^-C^alkylamino. f) Reactive dyes of the formula K? ip2 /% •v • / ^ / \ ^ \ • • II I • • so3h ho;js/ (4) , wherein Z^ and Z^ are as defined in e) g) Reactive dyes of formula (4), wherein and are 0-hydroxyethyl-arr.inc, X,N-di-$-hydroxyethy1amino, N-methyl-N-ji-hydroxyethylamino, N-ethyl-N-(3-hydroxyethylamino, tri (hydroxymethyl )methylamino or S-phenyl-N-p-hydroxyethylamino , provided that and Z^ cannot be Identical radicals selected from yS-hydroxyethyl^mino and N, N-di-^J-hydr oxye thy 1 amino.
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 l-amino-8-hydroxynaphthalene-4,6-disulfonic acid, benzenediazo components (A) and (B), 2,4,6-tri-chloro-s-triazine and amino compounds (Z^) and/or (Z^)* As the individual process steps referred to above can be carried out • in varying sequence and, if desired, 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 s sequence of the simple reactions between the individual reactants conveniently being chosen in accordance with the special conditions. It is known to carry cut coupling first in acidic medium in the o-amino position and then in alkaline medium in the o-hydroxy position 5 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 10 disazo compound of the formula h2'\ «? Fa /"z < >—; ; ?—< > (6) XS03H H03S/ V N./ XS03H H03S/ and condensing the resultant diprimary condensation product in the molar ratio of 1:2 with an equimolar mixture of amines (Z^) and (Z^) to give a reactive dye of formula (4); 15 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 reactive dye of formula (4), (Z^ = Z^); 3) condensing 2 mol of 2,4,6-trichloro-s-triazine with 1 mol of a 20 disazo compound of formula (6) and condensing the resultant diprimary condensation product with 2 mol of an amine (Z^) or (Z^) to give a reactive dye of formula (4), (Z^ = Z^)J 4) condensing 2 mol of 2,4,6-trichloro-s-triazine with 2 mol of l,3-phenylenediamine-4-sulfonic acid, condensing the primary conden- 25 sation product with 2 mol of an amine ^ ) or (Z^), diazotising the 7 resultant secondary condensation product and then effecting coupling, first in strongly acidic solution and then in neutral solution, with l-amino-S-hydroxynaphthalene-3,6-disulfonic acid to give a reactive dye of formula (4), (Z^ = Z^); It 5 5) condensing 2 mol of 2,4,6-trichloro-s-triazine with 2 mol of 1,3-phenylencdia:nine-4-sulfonic acid, diazotising the primary conden-S3tion product and then effecting coupling, first in strongly acidic solution and then in neutral solution, with l-amino-8-hydroxynaphtha-lene-3,6-aisulfonic acid, and condensing the resultant disazo dye with 10 2 col of an amine (Z^) or (Z^) to give a reactive dye of formula (4), (2i * V- 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. 15 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 subsequently reducing the nitro groups or by coupling 1,8-amino-naphthol-3,6-disulfonic acid with 2 equivalents of diazotised 5-acetyl-20 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 25 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 30 saponification with sodium hydroxide.
It is preferred to carry our the condensation of the 2,4,6-trichloro-s-triazine with the amines (Zj) and/or (2^) 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 formula (1) are listed individually below: Coupling components: l-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H acid), l-amino-8-hvdroxynaphthalene-4,6-disulfonic acid (K acid).
Diazo components: 1,3-diaminobenzene, 1,4-diaminobenzene, l,3-diamino-4-chlorobenzene, 1.3-diamino-4-methylbenzene, l,3-diamino-4-ethylbenzene, 1,3-diamino-4-methoxybenzene, l,3-diamino-4-ethoxybenzene, l,4-diaraino-2-methyI-benzene, 1,4-diamino-2-methoxybenzene, 1,4-diamino-2-ethoxybenzene, 1.4-diamino-2-chlorobenzene, 1,4-diamino-2,5-dimethylbenzene, l,4-diamino-2,5-diethylbenzene, 1,4-diamino-2-methyl-5-me thoxybenzene, 1,4-d iamino-2,5-dimethoxybenzene, 1,4-d iamino-2,5-die thoxybenzene, 1.3-diamino-2,4,6-trimethylbenzene, 1,4-diamino-2,3,5,6-tetrame thyl-benzene, 1,3-diamino-4-nitrobenzene, l,4-diaminobenzene-2-sulfonic acid, 1.4-diaminobenzene-2,5-disulfonic acid, 1,4-diaminobenzene-2,6-disulf onic acid, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonic acid, l,4-diamino-2-chlorobenzene-5-sulfonic acid, l,4-diamino-2-methylbenzene-5-sulfonic acid, l,5-diamino-6-methyl-benzene-3-sulfonic acid, l,3-diamino-6-methylbenzene-4-sulfonic acid, l,4-diaminobenzene-2-carboxylic acid, 1,3-diaminobenzene-4-carboxylic acid, 1,2-diaminobenzene-4-carboxylic acid, 1,3-diaminobenzene-5- 9 carboxylic acid, l-amino-3-nitrobenzene-6-sulfonic acid or l-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-5 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-aainobenzene-2-sulfonic acid or l-snino-4-acetyla:ninobenzene-3-sulfonic acid, l-amino-3-acetyianiinobenzene-i-sulfonic acid or 10 l-amino-3-acetylaminobenzene-6-sulfonic acid, l-amino-3-acetylanino-benzene-4,6-disulfonic acid, l-amino-4-acetylaminobenzene-2,5-disulfonic acid or l-amino-4-acetylaainobenzene-2,6-disulfonic acid, l-amino-3-acetylamino-4-methylbenzene-6-sulfonic acid.
Reactive component: 15 2,4,6-trichloro-s-triazine (cyanuric chloride).
Amines (Z^) and (Z^): methoxyethylamine, ethoxyethylamine, methoxypropylamine, chloroethyl-arnine, hydroxyethy1amine, N,^-di-^-hydroxyethylanine, hydronypropylaaine, 3-sulfatoethylamine, N-phenyl-N-p-hydroxy- 20 ethylamine, N-methyl-N-p-hydroxyethylamine, N-ethyl-N-p-hydroxyethyl-amine, trHhydroxymethyDmethylamine.
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 pclyurethanes, and especially cellulosic fibre materials 25 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 10 and which are components of blended fabrics, e.g. of blends of cotton with polyester or polvamidc fibres.
The dyes of this invention can be applied in different manner to the fibre material and fixed thereon, especially in the fortn of aqueous 5 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 arc 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 10 the application of heat. The dyes of this invention are also particu larly 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 snoring the impregnated goods for several hours at room temperature. After fixation the dyeings or prints are 15 thoroughly rinsed with cold and hot water, if necessary with the addition of a compound which acts as a dispersant and piromotes 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. 20 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 25 cellulosic fabrics have excellent 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 30 rubbing. 11 10 15 The invention is illustrated by the following Examples in which parts and percentages are by weight, unless otheri^ise stated. The ratio of parts by weight to parts by volume is the same as that of kilograms to litres.
The preparation of the tnonoazo 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 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 of cyanuric chloride 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 1-n sodium hydroxide. When acylation of the two terminal amino groups is complete, 9 parts of N-^>-hydroxyethylanilin2 are added to the 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 \ /\ V SO^H HO^S' S03H H03S' KOCH.C 2 ■CH CH OH 1 2 dyes cotton by the exhaust process in navy blue shades.
Similar dyes are obtained by carrying out the amidation in this Example replacing N-^-hydroxycthylaniline by the corresponding amount of one of the following amines: X-methylethanolamine CH3~XK-CH.,CK,OH N-c thy1e thano1aaine CH3 CK 2»XH-CH,CH ?OH CH,OH tris(hydroxyraethyl) arninome thane H^N-C^—CH^OH \_:.2 C?-2OH I 13 Example 2 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 l-amino-S-'nydroxy-5 naphthalene-3,6-disulfonic acid, and coupling the diazotised diazo component indicated in column 3 to the r.onoazo compound so obtained.
Tal.le 1 No.
Diazo component Diazo component Shade 1 2-(3'-amino-4'-sulfopheny1amino)-4-chloro-6-(/3-hydroxyethylamino)-1,3,5-triazine 2-(31 -a.uino-4 '-su1fophcnyI amino) -4-clilor Diazo component Diazo component Shade 4 2—( 4' -aniino-3' -sul fopheny1amino)-4-ch lor o-6-( ethoxy ethyl amino)-1,3,5-triazine 2-(4' - amino-3 '-sul to pheny lamino) -4-chl orcr6-(ethoxyethylamino)-l,3,5-triazine i;rocni sh navy blue 5 5 2-(4*-anino-3'-sulfophenylamino)-4-chloro-6-(N-ethyl-N-0-hydroxyethyl-amino)-l,3,5-triazine 2-(4'-amino-3'-su1fophenylamino)-4-clil oro-6-( N-e thy I-N-fl-hydroxy ethy 1-amino)-l,3,5-triazine do 10 6 2-(4 '-anti no-3*-sul f opheny 1 amino)-4-ch loro-6-l. W-pheny 1-N-^-hydroxyethy 1-amino)-l,3,5-triazine 2-(4'-amino-3'-sulfophenylamino)-4-chloro-6-(N-phenyl-N-^-hydroxyethyl-amino)-l,3,5-triazine do 7 2-(3'-amino-4' -sulf opheny lamino) -4-ch I oro-6-( N, N-'ii-^}-hydro::yethylr.inino)-1,3,5-triazine 2—(3'-amino-4'-sulfophenylamino)-4-ch lor o-6-(/5-hydroxy ethy lamino) - 1,3,5-triazine navy blue 15 8 2—(3'-amino-41-su1fophenylamino)-4-ch loro-6-(N-phenyl-N-p-hydroxyethyl-ami no)-1 ,3,5-triazine do do 9 2 — (3' -iiniino-4' -sul fophenylamino)-4-chloro-6-(N-ethy1-N-p-hydroxyethyl-amino)-l,3,5-triazine do do do No.
Diazo component Diazo component Shade 10 2-(3'-amino-4 ' -ai'.l fophenylamino)-4-chloro-6-^-hydroxyethylamino)-1,3,5-triazine 2-(4'-omino-3'-su1fopheny1 amino)-4-chl o r o-6-(H, N-d i-/£-hyd r o:cy ethyl ami no)-1,3,5-tr iazine navy blue 5 1 1 do 2-(41-ami no-3'-suIfopheny1 amino)-4-cltl oro-6-(ethoxye thy lamino)-1,3,5- triazine do 10 12 do 2-(4'-amino-3'-sulfopheny1 amino)-4-ch loro-6 - (N-e thy l-N-p-hydroxyc thy 1-amino)-l,3,5-triazine do 13 do 2-(4 1 -uinino-3' - su 1 fopheny lamino) - 4-chl oro-6-(N-pheny1-N-p-hydroxye thyl-amino)-1,3,5-triazine do 15 14 2-(4 '-aminor:2 ' , 5'-disulfopheny1-amino)-4-chloro-6--hyd r o:cy ethyl ami no)-1,3,5-triazine do No.
Diuzo component Diazo component Shad'; 15 2-(4' - .inino — 2' , 5' -disu 1 fopheny 1-amino) -A- dilorcrO>-(p-hydroxy ethyl-amino)-1,3,5-triazine 2-(3'- ami no-A'-su1fophenyI amino)-A-ch 1 or(r6-(N-pheny1-N-p-hydroxyethyl-ami no)-1,3, 5-tr iaz ine navy blue 5 16 do 2-(3'- ;unino-A'-sulfophenyI ami no)-4-ch lor o-6-(N-ethy1-N-p-hydroxyethy1-amino)-1,3,5-triazine do 10 17 2-(3' -ami no-A' -sulfophenylamino)-A-clil o rcr 6-(N-phcnyl-N-p-hydroxy ethyl-ami no)-1,3,5-tr iaz ine 2-(A 1 -amino-2',5'-disulfophenylamino)-A-ch 1 or o-6-(^5-hydroxy ethyl amino)-1,3, 5-triazine do 18 1 2-(3' -amino-A' -sulfophenylamino)-A-ch I o ro-6-(N-ethy1-N-p-hydroxyethy1-amino)-1,3,5-triazine do do 18 Dyeing Procedure 1 2 parts of che dye obtained in Example 1 are dissolved at 20° to 50°C 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 5 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 210°C, subsequently soaped for a quarter of an hour in a 0.1 Z boiling solution of a non-ionic detergent, rinsed and dried.
Dyeing Procedure 2 10 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 15 sodium hydroxide solution (36° Be) are added. The temperature is kept for a further 45 to 60 minutes at 75° to 80°C and the fabric is then soaped for 15 minutes in a 0.1 Z boiling solution of a non-ionic detergent, rinsed and dried.
Dyeing Procedure 3 20 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 Z and then dried.
The fabric is then impregnated with a solution having a temperature of 20°C 25 which contains 5 g/1 of sodium h^idroxide and 300 g/1 of sodium chloride, and then expressed to a pick-up of 75 Z. The dyeing is steamed for 30 seconds at 100° to 101"C, rinsed, soaped for a quarter of an hour in a 0.3 Z boiling solution of a non-ionic detergent, rinsed and dried.
Dyeing Procedure A 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 60°C and AO 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 60°C. 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 A5 parts of 5 % sodiun 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 A to 8 minutes at 100°C 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 (16)
1. CLAIMS: 20 1. A rcactivc* dye of the formula H? y»2 ». • • • A ^ \ ^ ji Z.-f j[-NH-?-A [~li ~ N_* » *~~N = K""» B-t-NH-C/ \-Z \) \\ "0SAA# V • H-<3S2 • -\O3H <4>0-2 V CI 3 CI (1) , wherein each of Z^ and Z^ independently of the other is a radical 5 of the formula -N^1 (2), 2 is alkyl v'nic'n cay be substituted by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, carboxy, cyano, chlorine vr sulfato, and R? is hvorogen, alkyl which may be substituted by hydroxy, 10 alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, carboxy, cyano, chlorine or sulfato, or is phenyl, benzyl or phenethyl, the benzene ring of which may be substituted by methyl, methoxy, acetyl-amino, chlorine, bromine, carboxy or sulfo and the benzene rings A and B may be further substituted, provided that, when R2 is phenyl, then Rj 15 is alkyl which is substituted by hydroxy, alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy. carboxy. cyano. chlorine or sulfato; and further provided that the coirjcunds of formula I are excluded vhareinZj and Z, are identical radicals selected from g-hydroxyethy1-, g-hydroxypropy1-, 20 X "hydroxypropyl-, -dihydroxypropyl-, £<-hydroxymethyl-p-hydroxy)- ethyl-, ^-methoxyethvl-, ^j*-methoxypropyl-, -ethoxypropyl-, ft -<^>'-hydroxyethoxy)ethyl-, y -(^}'-hydroxyethoxy)propyl-, N,N-di-jf>-hydroxyethyl-, N-/-hydroxyethyl-N-p-hydroxypropyl-, N-tS-cyano-ethyl-N-^-^'hydroxvet/ioxy)ethyl-> N-ethyl-N-tyJ-hydroxypropyl)-, 25 N-raethyl-N-^J JT-dihydroxypropyl)- And N-n-prppyl-N-(yj^T-dihydroxypropyl) -amino.
2. A reactive dye according to claim 1, wherein the coupling component is l-amino-8-hydroxvnaphthalene-3,6-disulfonic acid, and Z^, Z^» A and B are as defined in claim 1. 30 3.
3. A reactive dye according to claim 2, wherein Zhas the same meaning as Z^, and the benzene rings A and B contain no further substituents apart from 0 to 2 sulfo groups. I.
4. A reactive dye according to claim 3, wherein each of the benzene rings A and B contains a sulfo croup.
5. A rcactive dye according to claim 1, of the formula f2 7 -A. rA s - A.A s . s A. A 2l~f S-N~ ■' 12 1 ! fi-z2 V n-\o3h »/ v v v ^ y 1 (3) , " wherein Z^ and are as defined in clain 1.
6. A reactive dye according to claim 5, wherein Z^ and Z^ are hydroxy-C^-C^alkylamino, N-C^-C,alkyl-N-hydroxy-C^-C^alkylamino, N,N-dihydroxy-C^-C^alkylamino or N-phenyl-N-hydroxy-C^-C^alkylamino.
7. A reactive dye according to claim 6, of the formula H? f2 \ 4 \ / \ / \ ^ \ / \ & Vy S03H H03S N» SO H H03S Y (A) > wherein Z^ and are as defined for claim 6.
8. A reactive dye according to claim 7, wherein Z^ and are p,-hydroxy ethy lamino, N,N-di-f3-hydroxve thy lamino, NT-methy l-N-(3-hydroxyethylamino, X-et'nyi-N-p-hydroxye thy lamino, tri(hydroxymethyl)-niethvlaiaino or N-phenyl-N-j3-hydroxyethylanino , provided that Zj and Z» cannot be identical radicals selected from £-hydroxyethylamino £ i and N,N-di-^>-hydroxye thy lamino.
9. A process for the preparation of a reactive dye according to claim 1, which process comprises coupling and condensing, in suitable sequence, l-amino-S-hydroxynaphthalene-3,6-disulfonic acid or l-amino-8-hydroxynaphthalene-4,6-disulfonic acid, benzenediazo components (A) and (B), 2,4,6-trichloro-s-triazine, and amino compounds (Z^) and/or (Z^)*
10. A process for dyeing or printing textile fibre material, which comprises the use of a reactive dye according to claim 1.
11. A process according to claim jo for dyeing cellulosic fibres, especially cotton.
12. A reactive dye of the formula (I) as claimed in claim 1 substantially as hereinbefore described and exemplified.
13. A process for the preparation of a reactive dye of the formula (I) as claimed in claim 1, substantially as hereinbefore described and exemplified.
14. A reactive dye of the formula (I) as claimed in claim 1 whenever prepared by a process claimed in claim 9 or 13.
15. A process according to claim 10 for dyeing or printing textile fibre material, substantially as hereinbefore described and exemplified.
16. Dyed or printed textile fibre material whenever obtaine by a process claimed in any one of claims 10, 11 or 15. F. R. KELLY & CO., AGENTS FOR THE APPLICANTS.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH320184 | 1984-07-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE851409L true IE851409L (en) | 1986-01-03 |
| IE57997B1 IE57997B1 (en) | 1993-06-02 |
Family
ID=4250843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE1409/85A IE57997B1 (en) | 1984-07-03 | 1985-06-05 | Reactive dyes,process for their preparation and use thereof |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0170612B1 (en) |
| JP (1) | JPS6121164A (en) |
| KR (1) | KR930009899B1 (en) |
| AR (1) | AR242420A1 (en) |
| AT (1) | ATE43356T1 (en) |
| AU (1) | AU4444685A (en) |
| BR (1) | BR8502804A (en) |
| CA (1) | CA1243308A (en) |
| DE (1) | DE3570451D1 (en) |
| DK (1) | DK239985A (en) |
| ES (1) | ES8703917A1 (en) |
| GB (1) | GB2162193B (en) |
| GR (1) | GR851373B (en) |
| IE (1) | IE57997B1 (en) |
| IL (1) | IL75471A0 (en) |
| PT (1) | PT80739B (en) |
| TR (1) | TR23052A (en) |
| ZA (1) | ZA854248B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3443962A1 (en) * | 1983-12-10 | 1985-06-20 | Sandoz-Patent-GmbH, 7850 Lörrach | Reactive disazo compounds |
| 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 |
| 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 |
Family Cites Families (7)
| 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 |
| FR1543282A (en) * | 1966-08-01 | 1968-10-25 | Ici Ltd | Water soluble azo dyes and method of manufacture |
| 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 |
-
1985
- 1985-05-29 DE DE8585810248T patent/DE3570451D1/en not_active Expired
- 1985-05-29 DK DK239985A patent/DK239985A/en not_active Application Discontinuation
- 1985-05-29 EP EP85810248A patent/EP0170612B1/en not_active Expired
- 1985-05-29 AT AT85810248T patent/ATE43356T1/en not_active IP Right Cessation
- 1985-06-05 IE IE1409/85A patent/IE57997B1/en not_active IP Right Cessation
- 1985-06-05 ZA ZA854248A patent/ZA854248B/en unknown
- 1985-06-05 ES ES543896A patent/ES8703917A1/en not_active Expired
- 1985-06-06 GB GB08514298A patent/GB2162193B/en not_active Expired
- 1985-06-06 CA CA000483299A patent/CA1243308A/en not_active Expired
- 1985-06-06 GR GR851373A patent/GR851373B/el unknown
- 1985-06-07 AR AR85300667A patent/AR242420A1/en active
- 1985-06-10 IL IL75471A patent/IL75471A0/en unknown
- 1985-06-12 BR BR8502804A patent/BR8502804A/en not_active IP Right Cessation
- 1985-06-13 TR TR29310/85A patent/TR23052A/en unknown
- 1985-06-21 KR KR1019850004410A patent/KR930009899B1/en not_active IP Right Cessation
- 1985-06-28 PT PT80739A patent/PT80739B/en unknown
- 1985-07-01 AU AU44446/85A patent/AU4444685A/en not_active Abandoned
- 1985-07-03 JP JP60144851A patent/JPS6121164A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| ZA854248B (en) | 1986-02-26 |
| EP0170612A1 (en) | 1986-02-05 |
| ES543896A0 (en) | 1987-03-01 |
| GB2162193B (en) | 1988-11-02 |
| ES8703917A1 (en) | 1987-03-01 |
| PT80739A (en) | 1985-10-01 |
| JPH0246621B2 (en) | 1990-10-16 |
| ATE43356T1 (en) | 1989-06-15 |
| AU4444685A (en) | 1986-01-09 |
| EP0170612B1 (en) | 1989-05-24 |
| JPS6121164A (en) | 1986-01-29 |
| IE57997B1 (en) | 1993-06-02 |
| DK239985D0 (en) | 1985-05-29 |
| KR860001154A (en) | 1986-02-24 |
| BR8502804A (en) | 1986-05-27 |
| AR242420A1 (en) | 1993-03-31 |
| DE3570451D1 (en) | 1989-06-29 |
| GR851373B (en) | 1985-11-25 |
| PT80739B (en) | 1987-10-20 |
| TR23052A (en) | 1989-02-14 |
| IL75471A0 (en) | 1985-10-31 |
| GB8514298D0 (en) | 1985-07-10 |
| CA1243308A (en) | 1988-10-18 |
| DK239985A (en) | 1986-01-04 |
| KR930009899B1 (en) | 1993-10-13 |
| GB2162193A (en) | 1986-01-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Patent lapsed |