IE57997B1 - Reactive dyes,process for their preparation and use thereof - Google Patents
Reactive dyes,process for their preparation and use thereofInfo
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- IE57997B1 IE57997B1 IE1409/85A IE140985A IE57997B1 IE 57997 B1 IE57997 B1 IE 57997B1 IE 1409/85 A IE1409/85 A IE 1409/85A IE 140985 A IE140985 A IE 140985A IE 57997 B1 IE57997 B1 IE 57997B1
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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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- Organic Chemistry (AREA)
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- 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. wherein each of Z1 and Z2 independently of the other is a radical of the formula 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.
Description
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. -1- 5 ? y '< *> The present invention relates to reactive dyes and to the use thereoffor dyeing or printing textile fibre materials.
Specifically, the present invention relates to reactive dyes of theformula H? ^2 /.%—N = N—/ x/ ;; = n—/ \ . B—(ray Yz2 A . · ''f E_NH~V ' ’ k · k V '·Μί'νχν Cl 3 (1) > (S 3 0-2 Λ Cl wherein each of and independently of the other is a radicalof the formula -< (2), is alkyl which may be substituted by hydroxy, alkoxy, hydroxyalkoxy, 10 alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, carboxy, cyano, chlorine or sulfate, and is hydrogen, alkyl which may be substitutedby hydroxy, 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 15 methyl, methoxy, acetylamino, chlorine, bromine, carboxy or sulfo, and the benzene rings A and B may be further substituted; provided thatwhen is phenyl, then R} is alkyl which is substituted by hydroxy,alkoxy, hydroxyalkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy,carboxy, cyano, chlorine or sulfato; and further provided that the 2Q compounds of formula 1 are excluded wherein Zj and are identical radicalsselected from β-hydroxyethyl-, β-hydroxypropy1-, % -hydroxypropyl-, Y -dihydroxypropyl-, 6<-hydroxymethyl-p-hydroxy)-ethyl-,yj-methoxyethyl-, Jf-methoxypropyl-, y -ethoxypropyl-,f> -(yo’-hydroxyethoxy)ethyl-, y -(β’-hydroxyethoxy)propyl-, N,N-di-£- 25 hydroxyethyl-, N-^-hydroxyethyl-N-p-hydroxypropyl- , N-jS-cyano- ethvl-N-^-GS’hydroxyethoxy)ethyl- » N-ethyl-N-(£-hydroxypropyl)-, N-methyl-N-(Α,Υ-dihytlroxypropyl)- and N-n-propyl-N(^,5-dihydroxypropyl)amino.
The substituent Rj is straight chain or branched and preferably contains I to 6 carbon atoms. Examples of are che following substituents: carboxvmethyl, β-carboxyethyl, β-carboxypropyl, methoxy-carbonyimet’nyl, ethoxvearbonylmethyl, β-methoxyethyl, β-ethoxyethyl,β-mcthoxvpropyl, β-chloroethy1, y-chloropropvl, I'-hydrexyethyl, y-hvdroxypropyl, β-hydroxybutyl, β-cyanoethyl, and fi-sulfatoethyl. If the substituent is an alkyl radical, it is straight chain or branched and likewise preferablycontains 1 to 6 carbon atoms; may be further substituted, asindicated above for formula (2). Examples of are: methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyland n-hexyl, 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 carbon atoms such as methyl, ethyl,propyl, isopropyl or butyl, alkoxy groups containing 1 to 4 carbonatoms 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 4carbon atoms such as methylamino, ethylamino, propylamino, isopropyl-amino or butylamino, alkoxycarbonyl containing 1 to 4 carbon atomsin the alkoxy moiety such as methoxycarbonyl or ethoxycarbonyl, alkyl-sulfonyl containing 1 to 4 carbon atoms such as methylsulfonyl orethyl sulfonyl, trifluoromethyl, nitro, cyano, halogen such asfluorine, chlorine or bromine, carbamoyl, N-alkylcarbamoyl containing1 to 4 carbon atoms in the alkyl moiety such as N-methylcarbamoyl orN-ethylcarbamoyl, sulfamoyl, N-alkylsulfamoyl containing 1 to 4 carbonatoms 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 substituentsmethyl, ethyl, methoxy, ethoxy, acetylamino, chlorine, bromine, ureido,hydroxy, carboxy or sulfomethyl. 4 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 arc meant those compounds which are ableto react with the hydroxyl groups of cellulose, with the amino, carboxyl, hydroxyl and thio groups of wool and silk, or vith the aminogroups and, if present, carboxyl groups of synthetic polyamides toform covalent chemical bonds.
Preferred embodiments of the reactive dyes of formula (1) are: 10 a) Reactive dyes of formula (1), wherein the coupling component isl-amino-8-hydroxynaphthalene-3,6-disulfonic acid, and Z^, Z^» A andB are as defined for formula (1). b) Reactive dyes of formula (1). wherein Z^ has the same meaning asZ^, and the benzene rings A and B contain no further substituents 15 apart from 0 to 2 sulfo groups. c) Reactive dyes of formula (1), wherein each of the benzene rings Aand B contains a sulfo group. d) Reactive dyes of the formula # \ \-N " N--N » N-·ζ Ζ,-<7 C-ΝΉ—tt- I I II I " " - k hoZv\A '1 • · II —I—NH-CT C-Z, SO^H 3 3 HC^S (3) . wherein Z^ and Z^ are as defined for formula (I). e) Reactive dyes of formula (3), wherein Z^ and Z^ are hydroxy-C^-C^ alkylamino, N-C,-C,alkyl-N-hydroxy-C,-C,alkvlamino, N,N-dihvdroxy-14 14 C^-C^alkylamino or N-phenyl-N-hydroxy-C^-C^alkylamino. f) Reactive dyes of the formula (4) , wherein Z^ and Z^ are as defined in e). g) Reactive dyes of formula (4), wherein Z^ and Z^ are β-hydroxyethyl-5 amino, X,N-di-3-hydroxyethylamino, X-methyl-X-^-hydroxyethylamino, N-ethyΙ-Ν-β-hydroxyethylamino, tri(hydroxymethyl)methylamino orS-phenyl-N-p-hydroxyethylamino , provided that Z and Z£ cannot beidentical radicals selected from yS-hydroxyethyLamino andN,N-di Important process variants comprise: 1) condensing 2 mol ofdisazo compound of the 2,4,6-trichloro-s-triazine with 1 mol of aformula /«2 • · · —· f . y_s = N_z y SO3H HO3SZ \z XSO3H H03SZ and condensing the resultant diprimary condensation product in themolar ratio of 1:2 with an equimolar mixture of amines (Z^) and (Z^)to give a reactive dye of formula (4); 2) condensing 2 mol of 2,4,6-trichloro-s-triazine with 2 mol of anamine (Z^) or (Z^) and condensing the resultant primary condensationproduct with 1 mol of a disazo compound of formula (6) to give areactive dye of formula (4), (Z^ = Z^); 3) condensing 2 mol of 2,4,6-trichloro-s-triazine with 1 mol of adisazo compound of formula (6) and condensing the resultant diprimarycondensation product with 2 mol of an amine (Z^) or (Z^) to give areactive dye of formula (4), (Z^ = Z^); 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-sation product with 2 mol of an amine (Z^) or (Z^), diazotising the resultant secondary condensation product and then effecting coupling,first in strongly acidic solution and then in neutral solution, withl-amino-S-hydroxynaphthalene-3,6-disulfonic acid to give a reactivedye of formula (4), (Z^ = Z^) ; 5) condensing 2 mol of 2,4,6-trichloro-s-triazine with 2 mol of1,3-phenvlencdiamine-4-sulfonic acid, diazotising the primary conden-sation product and then effecting coupling, first in strongly acidicsolution and then in neutral solution, with l-amino-8-hydroxynaphtha-lene-3,6-disulfonic acid, and condensing the resultant disazo dye with2 col of an amine (Z^) or (Z^) to give a reactive dye of formula (4), «1 - z2).
The procedure is the same when using l-amino-8-hydroxynaphthalene- 4,6-disulfonic acid as coupling component or where using other diazocomponents, 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 5-acetyl-aminoaniline-2-sulfonic acid and subsequently saponifying the acetyl-amino groups. In practice, the acid coupling is carried out by addinga solution of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid tothe strongly acidic diazo suspension. The subsequent alkaline coup-ling is effected in known manner in weakly alkaline medium. It ispreferred to carry out the coupling of the monoazo compound with afurther equivalent of the diazo components in alkaline bicarbonatesolution. The saponification of the two acetylamino groups aftercompletion of the alkaline coupling is carried out in known mannerwith alkaline compositions. It is preferred to carry out thesaponification with sodium hydroxide.
It is preferred to carry out the condensation of the 2,4,6-trichloro-s-triazine with the amines (Zp and/or and the disazo compound of formula (6) or the diazo components (A) and (B) in aqueous solutionor suspension, at low temperature and at a weakly acidic, neutral to " 5 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 ofreactive dyes of formula (1) are listed individually below: q 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, 15 1,3-diamino-4-methylbenzene, l,3-diamino-4-ethylbenzene, 1,3-diamino- 4-methoxybenzene, l,3-diamino-4-ethoxybenzene, l,4-diamino-2-methyl-benzene, 1,4-diamino-2-methoxybenzene, I,4-diamino-2-ethoxybenzene, 1.4- diamino-2-chlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 1.4- diamino-2,5-diethylbenzene, 1,4-diamino-2-methyl-5-methoxybenzene, 20 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-di- « sulfonic acid, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene- 25 4,6-disulfonic acid, l,4-diamino-2-chlorobenzene-5-sulfonic acid, 1.4- diamino-2-methylbenzene-5-sulfonic acid, l,5-diamino-6-methyl-benzene-3-sulfonic acid, l,3-diamino-6-methylbenzene-4-sulfonic acid, 1.4- diaminobenzene-2-carboxylic acid, 1,3-diaminobenzene-4-carboxylicacid, 1,2-diaminobenzene-4-carboxylic acid, 1,3-diaminobenzene-5- carboxylic acid, l-amino-3-nitrobenzene-6-sulfonic acid or1-amino-4-nitrobenzene-6-sulfonic acid.
If an aminoacetylamino compound is co be used as diazo componentinstead of a diamine, from which compound the acetyl group is subse-quently removed by saponification as explained above in thedescription of the process variants, it may be a monoacetyl compoundof one of the diazo components listed above, e.g. l-amino-4-acetyl-aainobenzene-2-sulfonic acid or l-amino-4-acetylaminobenzene-3-sulfonic acid, l-amino-3-acetylaminobenzene-4-sulfonic acid orl-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-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 (Z^) and (Z^): methoxyethylamine, ethoxyethylamine, methoxypropylamine, chloroethyl-amine, hydroxyethy 1 amine, N,£l-di-p-hydroxyethylanine,hydroxypropylamine, β-sulfatoethylamine, N’-phenyl-N-p-hydroxy- ethylamine, N-methyΙ-Ν-β-hydroxyethylamine, N-ethyΙ-Ν-β-hydroxyethyl-amine , tri(hydroxymethyl)methylam.ine.
The reactive dyes of formula (1) are suitable for dyeing and printinga very wide range of materials such as silk, leather, wool, polyamidefibres and polyurethanes, and especially cellulosic fibre materialsof all kinds. Examples of such fibre materials are natural cellulosefibres such as cotton, linen and hemp, as well as cellulose andregenerated cellulose. The reactive dyes of the formula (1) are alsosuitable for dyeing or printing fibres which contain hydroxyl groups 10 and which are components of blended fabrics, e.g. of blends of cottonwith polyester or polyamide fibres.
The dyes of this invention can be applied in different manner to thefibre material and fixed thereon, especially in the form of aqueousdye solutions and printing pastes. The reactive dyes of formula (1)are suitable both for the exhaust process and for dyeing by the paddyeing process, in which the goods arc impregnated with aqueous dyesolutions which may also contain salts, and the dyes are fixed aftertreatment with alkali, or in the presence of alkali, with or withoutthe 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 severalhours at room temperature. After fixation the dyeings or prints arethoroughly rinsed with cold and hot water, if necessary with theaddition of a compound which acts as a dispersant and promotes thediffusion of non-fixed dye. The reactive dyes of formula (1) arealso suitable for printing, especially on cotton, and for printingnitrogen-containing fibres, e.g. wool, silk or blends containing wool.
The reactive dyes of formula (1) are particularly suitable for dyeingby 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 oncellulosic fabrics have excellent tinctorial strength and excellentdye-fibre bond stability both in acidic and in alkaline medium, andthey also have good light fastness and very good wetfastnessproperties such as fastness to washing, water, sea-water, cross-dyeingand perspiration, as well as good fastness to pleating, ironing andrubbing. 11 The invention is illustrated by the following Examples in which partsand percentages are by weight, unless otherwise stated. The ratio ofparts by weight to parts by volume is the same as that of kilogramsto litres.
The preparation of the monoazo or disazo intermediates is not describedin all of the following Examples. However, any undisclosed preparationis clearly evident from what has been stated above.
Example 1: 21.5 parts of the disazo dye of the formula H2\ /\ ?U ΥΉ2 \ Μ V „ v. 5 r~N = N~r J [—N = N—.« τ xso3h ho3sz V A \o3h ho3sz 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-^-hydroxyethylaniline areadded to the dye suspension, the reaction mixture is heated to 40 to45eC and the pH is kept at 8 by the dropwise addition of a solutionof 1-n sodium hydroxide. Amidation is complete after 1 to 2 hours.
The dye is precipitated from the resultant solution by adding 10 7. by * volume of sodium chloride, then isolated by filtration and dried in vacuo at 60°C. · The resultant dye of the formula 1 2 dyes cotton by the exhaust process in navy blue shades.
Similar dyes are obtained by carrying out the amidation in this Examplereplacing N-^-hydroxyethylaniline by the corresponding amount of oneof the following amines: X-methylethanolamine CH^-NK-CH,C?\OH N-c thy1e thano1amine CH^CK ,CH? OH ^CH^OH tris(hydroxyraethyl) aminomethane H.X-C-—CH^OH CF-2OH * 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 monoazo compound so obtained.
Table 1 No. Diazo component Diazo component Shade 1 2-( 3 ’-amino-4'-sulfopheny1amino)-4-chloro-6-(β-hydroxyethylamino)-1,3,5-triazine 2-(3'-amino-4'-suIfophenyI amino)-4-chlor No. Diazo component Diazo component Shade 4 2-(41 -amino-3' — su 1 fopheny 1 ami no)-4-ch I or 0-6-( ethoxy ethyl amino)-1,3,5-triazine 2-(4' - amino-3 '-sul fo.pheny lainino) -4-chl orcr6-(ethoxyethylamino)-l,3,5-triazine greeni shnavy blue 5 2-(4'-amino-3 ’ -sul foplieny lamino)-4-chloro-6-(N-ethyΙ-Ν-β-hydroxyethyl-amino)-l,3,5-triazine 2-(4'- amino-3'-su1fophenyIamino)-4-clil oro-6-( N-e thy Ι-Ν-β-hydroxy ethy 1-amino)-l,3,5-triazine do 6 2-(4'-ami no-3'-sulfophenylamino)-4-chloro-6-V d-pheny1-N-^-hydroxyethy1-amino)-l,3,5-triazine 2-(4'-amino-3,-sulfophenylamino)-4-chIoro-6-(N-phenyl-N-^-hydroxyethyl-amino)-l,3,5-triazine do 7 2-(3'-amino-4'-sulfophenyl amino)-4-ch I or0-6-( N, N-diyJ-hyJro::yethylr.inino)-1,3,5-triazine 2-(3'-amino-4'-sulfopheny1amino )-4-ch lor 0-6-(/5-hydroxy ethyl amino)- 1,3,5-triazine navy blue 8 2-(31- amino-4'-sulfopheny1amino)-4-ch loro-6-(N-phenyl-N-p-hydroxyethyl-amino)-! ,3,5-triazine do do 9 2-(3'-amino-4'-sulfophenylamino)-4-chloro-6-(N-ethy Ι-Ν-β-hydroxyethyl-amino)-! ,3,5-triazine do do do c» No; Diazo component: Diazo component Shade 10 2-( 3’ -amino-4 ' -av.l fophenylamino)-4-chloro-6-^-hydroxyethylamino)-1,3,5-triazine 2-(4'-amino-3'-sulfophenylamino)-4-ch 1 oro-6-(H, N-di-/^-hydro:cyethy I ami no )-1,3,5-tr iazine navy blue 1 1 do 2-(4 ' -nmino-3' -sulfopheny1 amino) -4-cltloro-6-(e thoxye thylamino) -1,3,5-triazine do 12 do 2-(4’-amino-3*-su1fopheny1 amino)-4-cli loro-6-(N-e thy Ι-Ν-β-hydroxyc thy l-amino)-l,3,5-triazine do 13 do 2-(4 ' - a ini no-3 '-suIfophenyIamino)-4-chl oro-6-(N-phenyΙ-Ν-β-hydroxye thyl-amino)-1,3,5-triazine do 14 2-(4 '-aminos: 2 ' , 5' -disulfophenyl-amino)-4-chloro-6~95"hydroxyethyl-amino)-1,3,5-triazine 2-(3'-amino-4'-sulfopheny1 ami no)-4-chlor0-6-( lJ,N-di-/>-hydro:iyethylamino)-1,3,5-triazine do No. Diazo component Diazo component SIunle 15 2-(4'- anino-2 ' ,5'-d isul fophcnyl-amino)-4- dilortr6-(p-hydroxy ethyl-amino) -1, 3,5-tri azinc 2-(3' - a^ii no-4 ’ - su 1 f opheny I ainino) -4-cli 1 or Dyeing Procedure 1 2 parts of the dye obtained in Example 1 are dissolved at 20° to 50°Cin 100 parts of water with the addition of 5 to 20 parts of urea and2 parts of calcined sodium carbonate. A cotton fabric is impregnatedwith this solution to a pick-up of 60 to 80 Z and then dried. Thefabric 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 boilingsolution of a non-ionic detergent, rinsed and dried.
Dyeing Procedure 2 2 parts of the dye obtained in Example 1 are dissolved at 75eC in 2000 parts of water with the addition of 120 parts of sodium chlorideor calcined Glauber's salt. Then 100 parts of a cotton fabric areput into this dyebath and the temperature is kept' constant for 30 to60 minutes. Then 10 parts of calcined sodium carbonate and 4 ml ofsodium hydroxide solution (36° Be) are added. The temperature is keptfor a further 45 to 60 minutes at 75° to 80eC and the fabric is thensoaped for 15 minutes in a 0.1 Z boiling solution of a non-ionicdetergent, rinsed and dried.
Dyeing Procedure 3 2 parts of the dye obtained in Example 1 are dissolved in 100 partsof water while adding 0.5 part of sodium m-nitrobenzenesulfonate.. A cotton fabric is impregnated with this solution to a liquor pick-upof 75 Z and then dried.
The fabric is then impregnated with a solution having a temperature of 20°Cwhich contains 5 g/1 of sodium hydroxide and 300 g/1 of sodium chloride,and then expressed to a pick-up of 75 Z. The dyeing is steamed for30 seconds at 100° to 101’C, rinsed, soaped for a quarter of anhour in a 0.3 Z boiling solution of a non-ionic detergent, rinsedand dried. 1 9 Dyeing Procedure A 2 parts of the dye obtained in Example 1 are dissolved in 100 partsof water. The solution is added to 1900 parts of cold water, 60 partsof sodium chloride are added and 100 parts of a cotton fabric areput into this dvebath. The temperature is raised to 60°C and 40 partsof calcined sodium carbonate and another 60 parts of sodium chlorideare added after 30 minutes. The temperature is kept for 30 minutesat 60°C. The dyeing is rinsed and then soaped for 15 minutes in a0.3 7. 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 whichcontains 45 parts of 5 Z sodiun alginate thickening, 32 parts ofwater, 20 parts or urea, 1 part of sodium m-nitrobenzenesulfonateand 2 parts of sodium carbonate. A cotton fabric is printed with the printing paste so obtained on aroller printing machine. The printed fabric is steamed 4 to 8 minutesat 100°C in saturated steam, then thoroughly rinsed in cold and hotwater, in the process of which chemically nonfixed dye can be veryeasily removed from the fabric, and then dried. 4
Claims (16)
1. A reactive dye of the formula H? Nil < img-format="tif" img-content="drawing" /> Cl Cl (1) wherein each of and independently of the other is a radical5 of the formula < img-format="tif" img-content="drawing" /> 2. (4) , wherein Z^ and Z^ are as defined for claim 6.
2. A reactive dye according to claim 1, wherein the coupling componentis l-amino-8-hvdroxynaphthalene-3,6-disulfonic acid, and Z^, Z^» Aand B are as defined in claim 1. 30
3. A reactive dye according to claim 2, wherein Z^ has the same meaning as Z^» and the benzene rings A and B contain no further 21 substituents apart from 0 to 2 sulfo groups. k.
4. A reactive dye according to claim 3, wherein each of the benzenerings A and B contains a sulfo croup. (2), is alkyl which may be substituted by hydroxy, alkoxy, nvdroxyalkoxy alkvlcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, carboxy, evano, chlorineor culfato, and R? is hydrogen, alkyl which may be substituted by hydroxy, 10 alkoxy, hydroxyalkoxy, alkyl carbonyl, aikoxycarbonyl, 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 andB may be further substituted, provided that, when R£ is phenyl, then Rj 15 is alkyl which is substituted by hydroxy, alkoxy, hydroxyalkoxy, alkyl-carbonyl, aikoxycarbonyl, alkylcarbonyloxy. carboxy, cyano. chlorine orsulfato; and further provided that the compounds of formula I are excluded wherein Zj and Z? are identical radicalsselected from g-hydroxyethy1-, g-hydroxypropy1-, 20 X-hydroxypropyl-, y -dihydroxypropyl-, €<.-hydroxymethyl-p-hydroxy)-ethyl-,p-methoxyethyl-, -methoxypropyl-, y -ethoxypropyl-,ft -(^>’-hydroxyethoxy)ethyl-, y -(^}’-hydroxyethoxy)propyl-, N,N-di-^>-hydroxyethyl-, N-Z-hydroxyethyl-N-^-hydroxypropyl-, N-^£-cyano-ethyl-N-^-^'hydroxyethoxy)ethyl-» N-ethyl-N-tyl-hydroxypropyl)-, 25 N-raethyl-H-(y5JT-dihydroxypropyl)- And N-n-propyl-N-(jB^T-dihydroxypropyl) -amino.
5. A reactive dye according to claim 1, of the formula zV- Ύ .a. -Η- I • o SO H H? ?H2 A.A » · ·- It λ I* XH-Z \-Z i is 2 X = N- ( )( ( K0/V\AS0 Η· μπ A3 3 HC S y (3) , wherein Z^ and Z^ are as defined in claim 1.
6. A reactive dye according to claim 5, wherein Z^ and Z^ arehydroxy-C^-C^alkylamino, N-C^-C,alkyl-N-hydroxy-C^-C^alkylamino,Ν,Ν-dihydroxy-C^-C^alkylamino or N-phenyl-N-hydroxy-C^-C^alkylamino. 10
7. A reactive dye according to claim 6, of the formula < img-format="tif" img-content="drawing" /> HO3S • · • · · I I! I / \ / \ SO^H HO^S' AN“u «A / < img-format="tif" img-content="drawing" />
8. A reactive dye according to claim 7, wherein Z^ and Z^ arep-hydroxyethylamino, N,N-di-β-hydroxvethy1amino, N-methy1-Ν-β- 15 hydroxyethylamino, X-et’nyi-X-p-hydroxyethylaraino, tri(hydroxymethyl)-methvlamino or S-phenyl-N-p-hydroxyethylamino , provided that Zj and Ζ» cannot be identical radicals selected from ^-hydroxyethylaminoi t and N,N-diyS-hydroxyethy1amino. 22
9. A process for the preparation of a reactive dye according toclaim 1, which process comprises coupling and condensing, in suitablesequence, l-amino-S-nydroxynaphthalene-3,6-disulfonic acid or * l-amino-8-hydroxynaphthalene-4,6-disulfonic acid, benzenediazo 5 components (A) and (B), 2,4,6-trichloro-s-triazine, and amino compounds (Z,) and/or (Z.). A 12
10. A process for dyeing or printing textile fibre material, whichcomprises the use of a reactive dye according to claim 1.
11. , A process according to claim io for dyeing cellulosic fibres, 10 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 ofthe formula (I) as claimed in claim 1, substantially as 15 hereinbefore described and exemplified.
14. A reactive dye ofwhenever prepared by a the formula (I)process claimed as claimed inin claim 9 or c1 aim 1,13.
15. A process according to claim 10 for dyeing or printingtextile fibre material, substantially as hereinbefore 20 described and exemplified.
16. Dyed or printed textile fibre material whenever obtainedby 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 IE851409L (en) | 1986-01-03 |
| IE57997B1 true 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 |
|---|---|---|---|---|
| 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 |
| FR2556358B1 (en) * | 1983-12-10 | 1987-01-02 | Sandoz Sa | NOVEL BISAZOIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS DYES |
| 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 |
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 |
| EP0120807B1 (en) * | 1983-02-24 | 1989-01-18 | 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 EP EP85810248A patent/EP0170612B1/en not_active Expired
- 1985-05-29 AT AT85810248T patent/ATE43356T1/en not_active IP Right Cessation
- 1985-05-29 DK DK239985A patent/DK239985A/en not_active Application Discontinuation
- 1985-05-29 DE DE8585810248T patent/DE3570451D1/en not_active Expired
- 1985-06-05 ES ES543896A patent/ES8703917A1/en not_active Expired
- 1985-06-05 IE IE1409/85A patent/IE57997B1/en not_active IP Right Cessation
- 1985-06-05 ZA ZA854248A patent/ZA854248B/en unknown
- 1985-06-06 GR GR851373A patent/GR851373B/el unknown
- 1985-06-06 CA CA000483299A patent/CA1243308A/en not_active Expired
- 1985-06-06 GB GB08514298A patent/GB2162193B/en not_active Expired
- 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 |
|---|---|
| ATE43356T1 (en) | 1989-06-15 |
| TR23052A (en) | 1989-02-14 |
| GB8514298D0 (en) | 1985-07-10 |
| GR851373B (en) | 1985-11-25 |
| DE3570451D1 (en) | 1989-06-29 |
| KR930009899B1 (en) | 1993-10-13 |
| ES8703917A1 (en) | 1987-03-01 |
| KR860001154A (en) | 1986-02-24 |
| IE851409L (en) | 1986-01-03 |
| PT80739A (en) | 1985-10-01 |
| IL75471A0 (en) | 1985-10-31 |
| EP0170612A1 (en) | 1986-02-05 |
| BR8502804A (en) | 1986-05-27 |
| ZA854248B (en) | 1986-02-26 |
| EP0170612B1 (en) | 1989-05-24 |
| AU4444685A (en) | 1986-01-09 |
| GB2162193A (en) | 1986-01-29 |
| PT80739B (en) | 1987-10-20 |
| JPH0246621B2 (en) | 1990-10-16 |
| GB2162193B (en) | 1988-11-02 |
| DK239985D0 (en) | 1985-05-29 |
| CA1243308A (en) | 1988-10-18 |
| DK239985A (en) | 1986-01-04 |
| JPS6121164A (en) | 1986-01-29 |
| ES543896A0 (en) | 1987-03-01 |
| AR242420A1 (en) | 1993-03-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Patent lapsed |