GB1569233A - Dye formulations and dyes for cellulose or cellulosic fibrous material - Google Patents

Abstract

Textile materials made of cellulose and cellulose-containing fibre material are dyed with finely dispersed aqueous preparations which in addition to polyethylene glycol or boric esters of polyethylene glycol contain water-insoluble dyes of the formula I. The symbols in this formula are each as defined in Claim 1. The dyes of the formula I give dyeings and prints having very good fastness properties. <IMAGE>

Description

(54) DYE FORMULATIONS AND DYES FOR CELLULOSE OR CELLULOSIC FIBROUS MATERIAL (71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock Company of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The invention relates to aqueous dye formulations for dyeing or printing cellulose or cellulosic fibrous material and to certain dyes for use therein.The invention provides a dye formulation which in addition to one or more dispersing agents and water retention agents, water and optionally a disinfectant, contains one or more dyes devoid of sulfonic acid groups and having the general formula (I):

in which A is an unsubstituted or substituted anthraquinonyl, anthrapyridone or anthrapyrimidine, X is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical; B is hydrogen or an aliphatic radical; B' is an aliphatic, cycloaliphatic, araliphatic or aromatic radical; or the group

is a saturated five-membered, six-membered or seven-membered heterocyclic radical; and n is I or 2.

Radicals for A include monovalent and divalent cr-anthraquinonyl radicals which may bear one or more substituents in other a-positions and/or in the ss- position, a-anthrapyndone radicals and a-anthrapyrimidine radicals which may rear one or more substituents.

Examples of substituents which may be present in the monovalent or divalent cr-anthraquinonyl radicals are as follows: (a) for a-positions: hydroxy, C, to C4 alkoxy, amino, C, to C8 alkylamino, C, to C8 alkylamino bearing hydroxy, C, to C4 alkoxy, cyano or carbonylalkoxy of one to five carbon atoms as substituents, phenylamino, phenylamino bearing C, to C5 alkyl, methoxy. ethoxy, phenoxy, chloro or bromo as substituents, C, to C6 alkylthio, phenylthio.

phenylthio bearing C, to C5 alkyl as a substituent,

(in which R' is Ct to C5 alkyl), phenyl, or pheny bearing C, to C4 alkyl, bromo, chloro, methoxy or ethoxy as a substituent; the substituents in the a-positions being identical or different in cases where there is more than one substituent; (b) for p-positions:: chloro, bromo, methyl, ethyl, C1 to C6 alkoxy, phenoxy, alkylphenoxy of one to six carbon atoms in the alkyl, chlorophenoxy, bromophenoxy, C, to C6 alkylthio, phenylthio, alkylphenylthio of one to six carbon atoms in the alkyl, acetyl, propionyl, benzoyl, monomethylbenzoyl. dimethylbenzoyl, trimethylbenzoyl, phenoxybenzoyl, C, to Css alkoxycarbonyl, N-alkyl or N,N-dialkylaminocarbonyl of one to six carbon atoms in each alkyl, phenylaminocarbonyl, alkylphenylaminocarbonyl of one to six atoms in the alkyl, cyano, C, to C5 alkylsulfonyl, phenylsulfonyl, C, to C6 alkylphenylsulfonyl, N-alkylsulfamoyl or N,N-dialkylsulfamoyl of one to six carbon atoms in each alkyl, N-alkoxyalkylsulfamoyl or N,N-bisalkoxyalkylsulfamoyl of three to twelve carbon atoms in each alkoxyalkyl.

In one of the appositions or a-positions there may also be present a nitro group or in one p-position an oxadiazole or thiodiazole radical. The sum of the substituents in the a- and B-positions is from zero to 6.

The anthrapyridone radicals or anthrapyrimidine radicals may also if desired bear C, to C8 alkyl, hydroxy, amino, phenyl,

in which R' is as defined above, C, to C5 alkylphenyl, C, to C6 alkoxycarbonyl, C, to C4 alkylcarbonyl, benzoyl or cyano as a substituent. The number of substituents may be zero, 1 or 2 and particularly zero or 1.

Besides hydrogen, X may be for example the following substituents: linear or branched C, to C8 alkyl; C, to C8 alkyl bearing chloro, bromo, C, to C4 alkoxy, alkoxycarbonyl of a total of two to five carbon atoms, C, to C4 alkylsulfonyl and/or phenoxy as a substituent; cyclohexyl; araliphatic radicals such as phenalkyl of seven to ten carbon atoms; phenyl; naphthyl: phenyl or naphthyl bearing C, to C,8 alkyl, C, to C4 alkoxy, C2 to C4 hydroxyalkoxy, C, to C4 alkylthio, chloro, bromo.

trifluoromethyl, nitro, cyano, sulfamoyl, N-alkylsulfamoyl, N,N-dialkylsulfamoyl of one to eight carbon atoms per alkyl, carbamoyl, N-alkylaminocarbonyl, N,Ndialkylaminocarbonyl of one to eight carbon atoms per alkyl, carbonylalkoxy of a total of two to five carbon atoms, C, to C4 alkylsulfonyl or C, to C4 alkylcarbonyl as substituents; the number of substituents on the phenyl or naphthyl being from one to three, preferably one or two, and the substituents being identical or different.

Specific examples of radicals X other than those already specified are: (I) substituted or unsubstituted alkyl: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, hexyl, octyl, 2-ethylhexyl, 2-methoxyethyl, 2-ethoxyethyl, '- butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-propoxypropyl, 3-butoxypropyl.

phenoxymethyl, dichlorophenoxymethyl and p-methylphenoxymethyl; (2) phenalkyl of seven to ten carbon atoms, benzyl, phenylethyl, phenylpropyl and phenylbutyl; (3) substituted or unsubstituted phenyl and naphthyl: phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl.

propylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, sec.-butylphenyl, tert.-butylphenyl, octylphenyl, isooctylphenyl, (a'-ethylhexyl)-phenyl, decylphenyl, dodecylphenyl, octadecylphenyl; methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, propoxyphenyl, diisopropoxyphenyl, butoxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl. methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, N-methylsulfamoyl phenyf, N,N-dimethylsulfamoylphenyl, N-ethylsulfamoylphenyl, N-butylsulfamoylphenyl, N,N-dibutylsulfamoylphenyl, N-hexylsulfamoylphenyl, N.N dihexylsulfamoylphenyl, N-octylsulfamoylphenyl. N,N-dioctylsulfamoylphenyl. Nmethylaminocarbonylphenyl, N,N-dimethylaminocarb(1nylphel N-ethylamino carbonylphenyl, N,N-diethylaminocarbonylphenyl, N-butylaminocarbonylphenyl.

N,N-dibutylaminocarbonylphenyl, N-hexylaminocarbonylphenyl, N-octylamino- carbonylphenyl, cyanophenyl and nitrophenyl.

Preferred radicals for X are: methyl, ethyl, p-chlorophenyl, p-bromophenvl.

p-C, to C4 alkylphenyl such as p-methylphenyl, p-ethylphenyl, p-isopropylphenyl.

p-butylphenyl, p-tert.-butylphenyl, p-methoxyphenyl, p-ethoxyphenyl and m-N,N-bis C, to C4 alkylsulfamoylphenyl such as N,N-dimethylsulfamoylphenyl and N,N-diethylsulfamoylphenyl. Unsubstituted phenyl is particularly preferred for X.

Radicals for B, in addition to hydrogen, include: linear or branched C, to C4 alkyl; C, to C4 alkyl bearing hydroxy, cyano, chloro, bromo, carbonylalkoxy of a total of two to five carbon atoms, N-alkylaminocarbonyl or N,N-dialkylaminocarbonyl of one to eight carbon atoms per alkyl, C, to C4 alkylsulfonyl or phenoxy as substituents or alkoxyalkyl ot a total ot three to six carbon atoms.

Specific examples of radicals for B are: hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, 2-hydroxyethyl, 2-chloroethyl, 2bromoethyl, 2-(methyl))thio)-ethyl, 2-cyanoethyl, 2-(methoxycarbonyl)-ethyl. 2 (ethoxycarbonyl)-ethyl, 2-(butoxycarbonyl)-ethyl, 2-(methylsulfonyl)-ethyl and 2 (butylsulfonyl)-ethyl. B is preferably C, to C4 alkyl. Hydrogen is particularly preferred for B.

Examples of B' as aliphatic, cycloaliphatic. araliphatic or aromatic radicals are: (a) unsaturated or preferably saturated linear or branched C1 to C,8 alkyl; (b) C2 to C8 alkyl bearing hydroxy, cyano, chloro, bromo, carbonylalkoxy of a total of two to five carbon atoms, N-alkylaminocarbonyl or N,N-dialkylaminocarbonyl of one to eight carbon atoms per alkyl, C1 to C4 alkylsulfonyl, dialkylamino of one to four carbon atoms per alkyl or phenoxy, the number of substituents being two or preferably one; (c) alkoxyalkyl of a total of three to eleven carbon atoms; (d) hydroxyalkoxyalkyl of a total of four to ten carbon atoms; (e) phenoxyalkoxyalkyl of a total of ten to twelve carbon atoms:: (t) saturated five-membered, six-membered, seven-membered or eightmembered cycloalkyl or polycycloalkyl; (g) cycloalkyl optionally bearing one to three identical or different substituents selected from C, to C8 alkyl, cycloalkyl and hydroxyl; (h) phenalkyl of a total of seven to ten carbon atoms in which the alkyl radical may be substituted by hydroxy and the phenyl radical may be substituted by C, to C16 alkyl; (i) phenyl or naphthyl in which one to three, preferably one or two and particularly one hydrogen atom may be replaced by C, to C,8 alkyl, chloro, bromo, trifluoromethyl, nitro, cyano, C, to C5 alkoxy.C, to C4 alkylthio, sulfamoyl, Nalkylsulfamoyl or N,N-dialkylsulfamoyl of one to eight carbon atoms per alkyl, N- phenylsulfamoyl, carbamoyl, N-alkylaminocarbonyl or N,N-dialkylaminocarbonyl of one to eight carbon atoms per alkyl, carbonylalkoxy of a total of two to six carbon atoms, C, to C4 alkylsulfonyl, phenylsulfonyl optionally bearing alkyl as a substituent in the phenyl, C, to C4 alkylcarbonyl, phenalkoxy of seven to ten carbon atoms in which the phenyl radical may bear chloro, bromo or cyano as a substituent, phenoxy or 4-chlorophenoxy and therein the substituents may be identical or different and where when there is more than one alkyl or alkoxy, or alkyl and alkoxy, the sum of the carbon atoms in these substituents is not more than twe#ye.

Specific radicals B' other than those already specified include for example: .(1) unsubstituted or substituted alkyl: the alkyls specified for B and also n Fi,tyl, isoamyl, sec.-pentyl, neopentyl, n-hexyl, methylpentyl, dimethylbutyl, hep,tyl, methylhexyl, dimethylpentyl, trimethylbutyl, n-octyl, isooctyl, methyl hptyl, 2-ethylhexyl, dimethylhexyl, trimethylpentyl, tetramethylbutyl, n-nonyl, isononyl, dimethylheptyl, trimethylhexyl, decyl, undecyl, dodecyl, 2,2-dimethyldecyl, tetradecyl, hexadecyl, octadecyl, 2-hydroxyethyl, 3-hydroxypropyl, 2chloroethyl, 2-bromoethyl, 2-methylthioethyl, 2-butylthioethyl, 2-cyanoethyl, 2 (methoxycarbonyl)-ethyl, 2-(ethoxycarbonyl)-ethyl, 2-(butoxycarbonyl)-ethyl, 2 (methylsulfonyl)-ethyl. 2-(ethylsulfonyl)-ethyl, 2-(butylsulfonyl )-ethyl, 3-(N,Ndiethylamino)-propyl, 3-(N,N-dimethylamino)-propyl, 3-(N,N-dibutvlamino)propyl, 2-phenoxyethyl, 3-phenoxypropyl, 4-phenoxypropyl: 2-methoxyethyl, 2 ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3propoxypropyl, 3-butoxypropyl, 3-(2'-ethylhexoxy)-propyl; 2-(2'-hydroxyethoxy)ethyl, 2-(3'-hydroxypropoxy)-ethyl, 2-(4'-hydroxybutoxy)-ethyl, 3-(2'-hydroxyethoxy)-propyl, 3-(3'-hydroxypropoxy)-propyl, 3-(4'-hydroxybutoxy)-propyl, 2-(2'phenoxyethoxy)-ethyl, 3-(2'-phenoxyethoxy)-propyl, 2-(3'-phenoxypropoxy)-ethyl and 3-(3'-phenoxypropoxy)-propyl; (2) unsubstituted or substituted cycloalkyl or polycycloalkyl:

(3) unsubstituted or substituted phenylalkyl: -CH2-C8H5, -CM2-CH2-C5H5,

and the corresponding phenyl-substituted compounds in which -C8H5 is replaced by -C8H4-CH3; -CH2-C51114-C12 11125, -ClI2-C8H4C8H17 -CH2C5M4-C8H18 -CM2-C61114-C611113.

(4) unsubstltuted or substituted phenyl or naphthyl: phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl.

propylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl sec.-butylphenyl, tert.-butylphenyl, hexvlphenyl, octylphenyl, isooctylphenyl, dodecylphenyl, octadecylphenyl; chlorophenyl, 2,4-dichlorophenyl, 3,5-dichlorophenyl, bromophenyl; 3-trifluorophenyl, nitrophenyl, nitromethylphenyl; cyanophenyl, methylcyanophenyl; methoxyphenyl, dlmethoxyphenyl, ethoxyphenyl, propoxyphenyl.

diisopropoxyphenyl, butoxyphenyl, pentoxyphenyl, (2'-methoxyethyl)-phenyl, (2'propoxyethyl)-phenyl, (3'-methoxypropyl)-phenyl, (3'-propoxypropyl)-phenyl: methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, pentoxycarbonylphenyl, methoxyethylcarbonylphenyl; ethoxyethylcarbonylphenyl.

propoxyethylcarbonylphenyl; methylsulfonylphenyl, ethylsulfonvlphenf I. butyl sulfonylphenyl; phenylsulfonylphenyl, 4"-methylphenylsulfonvlphenyl N-methyl- aminocarbonylphenyl, N,N-dimethylcarbonylaminophenyl, N-ethylamino- carbonylphenyl, N,N-diethylaminocarbonylphenyl N-butylaminocarbonylphenyl N,N-dibutylaminocarbonylphenyl, N-hexylami nocarbonylphenyl, N-(''-ethyl- hexylamino)-carbonylphenyl;N-methylsulfamoylphenyl, N,N-dimethylsulfamo) phenyl, N-ethylsulfamoylphenyl, N,N-diethylsulfamoylphenyl, N-butylsulfamoyl phenyl, N,N-dibutylsulfamoylphenyl, N-pentylsulfamoylphenyl N-(2'-ethyl hexyl )- suli8moylphenyl, N-(2'-hydroxyethyl)-sulfamoylphenyl, N,N-bis-(''-hvdroxy- ethyl)-sulfamoylphenyl, N-(2'-cyanoethyl)-sulfamoylphenyl, N,N-bis-(2'-cyano- ethyl)-sulfamoylphenyl, N-(3-methoxypropyl)-sulfamoylphenyl, N-cyclohexyl- 1- sulfamoylphenyl, N-phenylsulfamoylphenyl, N-(methylphenyl)-sulfamoylphenyl: benzyloxyphenyl, (2'-phenylethoxy)-phenyl, (3'-phenylpropoxy)-phenyl. (4'phenylbutoxy)-phenyl; phenoxyphenyl, 2-chlorobenzyloxyphenyl, 4-chlorobenzyloxyphenyl, 2-cyanobenzyloxyphenyl: 4-phenoxyphenyl, 4-(4'-chlorophenoxy)-phenyl.

Of the radicals specified for B1 the following are preferred: linear or branched C1 to C8 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl.

heptyl, 1,1 3-trimethylbutyl, 1 -methylbutyl, 1,1 -dimethylpropyl, 2,3-dimethyipentyl-(3), octyl, 2-ethylhexyl; hydroxyalkyl of two to four carbon atoms such as '- hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl; alkoxyalkyl of a total of three to ten carbon atoms such as 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 3methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 2-(2'-methoxyethoxy)-ethyl. 2-(2'ethoxyethoxy)-ethyl, 2-(2'-methoxyethoxy)-propyl, 2-(2'-ethoxyethoxy)-propyl: hydroxyalkoxyalkyl of a total of four to eight carbon atoms such as 2-(2'-hydroxyethoxy)-ethyl, 2-(2'-hydroxypropoxy)-ethyl, 2-(3'-hydroxypropoxy)-ethyl, 3-(2'hydroxyethoxy)-propyl, 3-(3 '-hydroxypropoxy)-propyl, 3-(4'-hydroxybutoxy)propyl, 2-(4'-hydroxybutoxy)-ethyl; phenylalkyl of a total of seven to ten carbon atoms such as benzyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 4-phenylbutyl, 2-hydroxy-2-phenylethyl; phenoxyalkyl of two to four carbon atoms in the alkyl and phenoxyalkoxyalkyl of a total of four to six carbon atoms in the alkoxyalkyl (equal to a total of ten to twelve carbon atoms) such as 2-phenoxyethyl, 3phenoxypropyl, 2-(2'-phenoxyethoxy)-ethyl, 3-(2'-phenoxyethoxy)-propyl, 3-(3' phenoxypropoxy)-propyl; N,N-dialkyl aminoalkyl of a total of four to twelve carbon atoms in the alkyl such as N,N-dimethylaminoethyl, N,N-diethylaminoethyl, N,Ndibutylaminoethyl, N,N-dimethylaminopropyl, N,N-diethylaminopropyl, N.N- dibutylaminopropyl; cyclohexyl; phenyl or phenyl in which one to three hydrogen atoms have been replaced by C, to C4 alkyl, methoxy, ethoxy chloro or bromo and/or one hydrogen atom has been replaced by alkoxycarbonyl of a total of two to five carbon atoms, N-alkylaminocarbonyl of one to four carbon atoms in the alkyl, N,N-dialkylsulfamoyl of one to four carbon atoms per alkyl, phenoxy or benzyloxy such as 4-tolyl, 4-ethylphenyl, 2,5-dimethylphenyl, 2,4-dimethylphenyl, 4-butylphenyl, 4-tert.-butylphenyl, p-chlorophenyl, p-bromophenyl, 2-methyl-4-chlorophenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 3-methoxycarbonylphenyl, 3-ethoxycarbonylphenyl, 3-butoxycarbonylphenyl, 3-N-methylaminocarbonylphenyl. 3-Nethylaminocarbonylphenyl, 3-N-butylaminocarbonylphenyl. N,N-diethylsulfamoylphenyl, N,N-dimethylsulfamoylphenyl, N,N-dibutylsulfamoylphenyl. N ethyl-N-butylsulfamoylphenyl. Preferred examples of

are NH-CH(CH3)2, -NH3H7(n), -NM-C4H8(n), -NH-C5H1 (n), -NH-CH-C3H7(n), CH3

For tinctorial reasons and because of advantages in use those dyes are particularly preferred in which

is one of the following groups: -NH-CH(CH3)21 -NH-C3H7(n) , -NH-C4H9(n) , -NH-C5H11(n)

The group

may moreover be a five-membered, six-membered or seven-membered saturated heterocyclic radical.Specific examples are the radicals of pyrrolidine, piperidine, morpholine, thiomorpholine, piperazine, hexamethyleneimine, N-methylpiperazine or N-ethylpiperazine. Piperidine and morpholine are preferred.

Examples of substituted a-anthraquinonyl or ,l-anthraquinonyl having zero to six substituents for A are those having the general formulae:

In the formulae (IIa to (IId) hal, and R' to R11 present the following substituents: hal: chloro, bromo; m = 1, 2 or preferably 0 (zero);R': hydrogen, chloro, bromo, methyl, ethyl, C, to C8 alkoxy, phenoxy, alkylphenoxy of one to six carbon atoms in the alkyl, chlorophenoxy, bromophenoxy, C, to C, alkylthio, phenylthio, alkylphenylthio of one to six carbon atoms in the alkyl, acetyl, propionyl, benzoyl, methylbenzoyl, dimethylbenzoyl, trimethylbenzoyl, phenoxybenzoyl, C1 to C8 alkoxycarbonyl, N-alkylaminocarbonyl or N,N-dialkylaminocarbonyl of one to six carbon atoms per alkyl, phenylaminocarbonyl, alkylphenylaminocarbonyl of one to six carbon atoms in the alkyl, cyano, nitro, C, to C8 alkylsulfonyl, phenylsulfonyl, C, to C, alkylphenylsulfonyl, N-alkylsulfamoyl or N,N-dialkylsulfamoyl of one to six atoms per alkyl, N-alkoxyalkylsulfamoyl or N,N-bisalkoxyalkylsulfamoyl of three to twelve carbon atoms per alkoxyalkyl.R2: hydrogen, hydroxy, C, to C4 alkoxy, amino, C, to C8 alkylamino; C, to C8 alkylamino bearing hydroxy, C, to C4 alkoxy, cyano or carbonylalkoxy of one to five carbon atoms as substituents, phenylamino; phenylamino bearing C, to C5 alkyl, methoxy, ethoxy, phenoxy, chloro or bromo as substituents; C, to C5 alkylthio; phenylthio; phenylthio bearing C, to C5 alkyl as a substituent;

in which R12 is saturated linear or branched C, to C5 alkyl: phenyl; or phenyl bearing C, to C4 alkyl, bromo, chloro, methoxy or ethoxy as a substituent.R3 and R4: hydrogen, hydroxy, amino, C, to C4 alkoxy, linear or branched C, to C4 alkylamino;

in which R12 has the above meanings; the radicals R3 and R4 being identical or different; one of the radicals R3 and R4 may also be nitro.

R5: hydrogen or methoxy.

R: nitro or the groups specified for R7 in which case R7 and R6 may be identical or different.

R7: hydrogen, hydroxy, saturated linear or branched C, to C5 alkylamino in which the alkyl may bear C, to C4 alkoxy, hydroxy or cyano as a substituent.

R8: C1 to C5 alkylamino or hydroxy.

Rg: phenyl; phenyl bearing C, to C6 alkyl, C, to C4 alkoxy, chloro or bromo as a substituent; C, to C,0 alkyl; C, to C,0 alkyl in which one or two hydrogen atoms are replaced by chloro, bromo, hydroxy, cyano, C, to C4 alkoxy, dialkylamino of one to four carbon atoms per alkyl, carbamoyl, carbonylalkoxy of a total of two to nine carbon atoms, C, to C5 alkylthio, phenyl or phenoxy, one or two hydrogen atoms in the phenyl substituents being optionally replaced by chloro, bromo, C, to C4 alkyl, methoxy, ethoxy, alkoxy, carbonyl, alkylthio, alkylsulfonyl and/or N-alkylsulfamoyl of one to four carbon atoms per alkyl; C, to C5 alkylthio; C7 to C,0 phenylalkylthio; phenylthio; or phenylthio bearing chloro, bromo, C, to C4 alkyl, methoxy or ethoxy as a substituent.

R'O: phenyl, C, to C5 alkyl; C1 to C8 alkylthio; C3 to C8 alkoxyalkyl: C, to C5 alkylamino; methoxy; ethoxy; or phenylalkylthio of one to five carbon atoms in the alkyl.

R": amino or C, to C5 alkylamino.

Furthermore A may for example be a radical of the formula

In these formulae the radicals R13 to R15 have the following meanings: R'3: hydrogen, C, to C6 alkoxycarbonyl, C, to C4 alkylcarbonyl, benzoyl or cyano.

R'5: hydrogen, C, to C5 alkyl or phenyl; R14: hydrogen, C, to C5 alkyl, phenyl or C, to C5 alkylphenyl.

Preferred substituents are as follows: For R': hydrogen, bromo, chloro, acetyl, carbonylalkoxy of one to five carbon atoms in the alkyl, benzoyl, methylbenzoyl, dimethylbenzoyl, trimethylbenzoyl, methoxybenzoyl, ethoxybenzoyl phenoxybenzoyl, N-alkylaminocarbonyl of one to four carbon atoms in the alkyl such as N-propylaminocarbonyl, nitro, cyano, C, to C4 alkylsulfonyl such as methylsulfonyl, phenylsulfonyl, methylphenylsulfonyl, C, to C4 alkoxy such as methoxy; for R2: hydrogen, hydroxy, amino, C, to C4 alkylamino, such as methylamino.

isopropylamino, isobutylamino; phenylamino; phenylamino bearing as substituents C, to C5 alkyl, methoxy, ethoxy or C2 to C4 C-acyloxy, such as methylphenylamino, methoxyphenylamino or 4-acetoxyphenylamino: C, to C4 alkoxy such as methoxy; for R3 and R4: hydrogen, hydroxy, amino, the substituents being identical or different; for R5, R8 and R7: hydrogen; for R8: amino; for Rg: phenoxyalkyl of one to six carbon atoms in the alkyl such as phenoxymethyl, 3-phenoxypropyl, 5'-phenoxypentyl, 2'-(dichlorophenoxy)-ethyl, 4-chloro3-methylphenoxymethyl; phenalkyl of one to six carbon atoms in the alkyl such as 5'-(diphenyl)-pentyl, 3'-(4-methylphenyl)-propyl;C, to C5 alkyl such as methyl, ethyl, propyl, butyl and phenyl, for R'O: C, to C5 alkyl, C, to C8 alkylthio or phenalkylthio of two to four carbon atoms in the alkyl; for R": amino; for R13: hydrogen; for R'4: hydrogen, hydroxy, phenyl, C, to C3 alkylphenyl such as methylphenyl; halophenyl such as chlorophenyl; for R'b: hydrogen.

Formulations according to the invention are advantageously prepared by grinding a suspension of from 15 to 40 and preferably from 20 to 35 parts of dye (1), from 4 to 10 parts of dispersing agent, from 5 to 15 parts of water retention agent, and if required from 0.5 to 1.5 parts of disinfectant in 75.5 to 33.5 parts of water in a stirred ball mill, bead mill or sand mill until the particle size is about 0.5 micron or less. Dispersons which are stable in storage are thus obtained.

The dispersing agents used may be anionic and nonionic dispersing agents commonly used for the production of finely particled formulations of disperse dyes.

Examples of anionic dispersing agents are lignin sulfonates, salts of phenolformaldehyde-sodium sulfite condensation products (German Laid-Open Application DOS 23 01 638), salts of 2-naphthalenesulfonic acid-formaldehyde condensation products, salts of phenolsulfonic acid urea formaldehyde condensation products, and salts of condensation products from phenolsulfonic acid, urea and formaldehyde which have been subsequently condensed with phenol and formaldehyde.

Ethylene oxide and propylene oxide-ethylene oxide adducts are particularly suitable as nonionic dispersing agents. These are described for example in U.S.

2,979,528 and 3,841,888.

The amount of dispersing agent depends on the dye and on its concentration in the dispersion; as a rule the amount of dispersing agent is from 4 to 10% by weight based on the formulation.

Particularly suitable water retention agents include glycols such as ethylene glycol, propylene glycol, diethylene glycol and preferably dipropylene glycol. The amount used is generally from 5 to 15% and preferably from 8 to 12"b by weight based on the formulation.

Dyes of the formula (I) may be prepared by reacting a compound of the formula (V): A(NH2)n (V) with a chlorotriazine of the formula (Vl)

in which A, X, B and B1 have the above meanings in an inert solvent in the presence or absence of a base (method (a)). (a)).

Another method is by first reacting the compound A-NM2 unilaterally with 1 mole of a dichlorotriazine of the formula (VII):

and then replacing the remaining chlorine atom by the radical

in a conventional manner (method (b)). These reactions are also advantageously carried out in an inert solvent or diluent.

Examples of suitable inert solvents or diluents are aromatic hydrocarbons, aromatic chlorohydrocarbons, such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, other solvents being nitrobenzene and N,Ndialkylcarboxamides such as N,N-dimethylformamide or N-methylpyrrolidone.

Aprotic polar solvents such as N,N-dimethylformamide and N-methylpyrrolidone are particularly suitable for the unilateral reaction (method (b)).

In method (a) the reaction is carried out as a rule at temperatures of from 60 to 180"C. The reaction is over after from two to ten hours. The reaction product is isolated by a conventional method.

The unilateral reaction according to variant (b) is carried out at temperatures of from 400 to 1200C and preferably from 450 to 809C. I or 2 moles of the dichlorotriazine (VII) are used per mole of (V). The amount of (Vll) depends on whether A has one or two reactive amino groups and in the case of two reactive amino groups on whether both these groups or only one of them is to be reacted. The unilateral reaction is generally over within one hour to three hours in the polar aprotic solvent. The amount stoichiometrically required or an excess of the amine forming the basis of the radical B B' I is then added and the mixture is kept at 600 to 1800C and preferably at 700 to 130"C until all the chlorine has been exchanged.The reaction product is precipitated by dilution with water and then isolated from the reaction mixture.

Dye formulations which contain a dye or mixture of dyes of the formula (VIII):

as defined below and which corresponds to formula (I) wherein A = A1, X = Y, B = B3 and B' = B2, are valuable industrially and therefore preferred.

In the formula (VIII) A' is one of the radicals of the formulae

in which the substituents D, E, H', F, G and K stand for the following radicals: D: hydroxy; amino; C, to C4 alkylamino; phenylamino; phenylamino bearing methyl, methoxy, chloro or bromo as a substituent in the 4-position; alkylcarbonylamino of one to three carbon atoms in the alkyl; benzoylamino; E: acetyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, benzoyl, 4-methylbenzoyl, 2,4,6-trimethylbenzoyl. 4.intthoxybenioyl. 4-phenoxy- benzoyl, N-propylaminocarbonyl, nitro, cyano, methylsulfonyl phenylulfonyl 4 methylphenylsulfonyl, bromo, methoxy, 2-oxadiazolyl or 2-thiodiazolyl which bear in the 5-position the substituents specified for R8 and R'O; F: hydrogen; hydroxy; amino;C, to C5 alkylamino; G: hydroxy: amino; phenylamino; benzoylamino: alkylcarbonylamino of one to three carbon atoms in the alkyl; H': hydrogen; hydroxy; phenylamino; amino; one of the substituents G and H' may also be nitro; K: hydrogen, hydroxy, methyl, phenyl, 4-methylphenyl; 4-chlorophenyl; Y: in the formula (VIII): 4-chlorophenyl; 4-bromophenyl; 4-methoxyphenyl: 3,N,N- diethylsulfamoylphenyl, p-methylphenyl; p-isoprop) Iphenyl; methyl: ethyl: and particularly phenyl.

In the formula (VIII), B2 is C1 to C8 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-pentyl, I-methylbutyl, I,l-dimethylbutyl, 2,4-dimethyl- pentyl-(2), 2,3-dimethylpentyl-(3), hexyl, isohexyl, heptyl, isoheptyl, n-octyl.

isooctyl, 2-ethylhexyl; 2-hydroxyethyl; alkoxyalkyl of a total of three to seven carbon atoms such as methoxyethyl, ethoxyethyl, butoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl or 3-(4'-hydroxybutoxy)-propyl: phenalkyl of a total of seven to ten carbon atoms such as benzyl, 2-phenylethyl, 4 phenylbutyl-(2)- or 3-phenylpropyl; phenoxyalkyl of two to four carbon atoms in the alkyl such as 2-phenoxyethyl or 3-phenoxypropyl; phenoxyalkoxyalkyl of four to six carbon atoms in the alkoxyalkyl such as 2-(2'-phenoxy ethoxy)-eihyl or 3-(2'-phenoxyethoxy)-propyl; cyclohexyl: phenyl or phenyl in which one to three hydrogen atoms are replaced by methyl, methoxy, ethoxy.

chloro or bromo and the substituents may be identical or different, or one hydrogen atom is replaced by fluoro, trifluoromethyl, phenalkoxy of seven to eight carbon atoms, carbonylalkoxy of a total of two to five carbon atoms, alkylamino carbonyl or dialkylsulfamoyl of one to four carbon atoms per alkyl or phenoxy such as methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl, fluorophenyl, 2chloro-4-methylphenyl, 2-chlorotrifluoromethylphenyl, ethylphenyl, isopropylphenyl, bromophenyl, methoxyphenyl, ethoxyphenyl, 4-benzyloxyphenyl, 4-(2'chlorobenzyloxy)-phenyl, 4-(ss-phenylethoxy)-phenyl, 3-methoxycarbonylphenyl, 3-butoxycarbonylphenyl, 3-ethoxycarbonylphenyl, 3-N-methylaminocarbonyl- phenyl, 3-N-ethylaminocarbonylphenyl, 3-N-butylaminocarbonylphenyl, N,Ndimethylsulfamoylphenyl, N,N-diethylsulfam oylphenyl, N,N-dibutylaminosulfamoylphenyl or N-ethyl-N-butylsulfamoylphenyl and B3 is hydrogen or the group B'-N-B2 is a piperidine or morpholine radical.

Formulations which contain one or more than one dye of the formula (IX):

as defined below, and which corresponds to formula (I) wherein A = A2, X = Z, B H, B1 = B4 are particularly preferred for technical and tinctorial reasons.

In the formula (IX) A2 is a radical of the formula (Xa) or (Xc) in which D, E, F, G and H' have the following meanings: D: amino: E: acetyl, benzoyl, methoxy, bromo, phenylsulfonyl or p-methyl-phenyl sulfonyl; F, G and H': hydroxy or amino, one or two of the radicals F, G and H being hydroxy; Z: 4-chlorophenyl, 4-methoxyphenyl, 4-methylphenyl and preferably phenyl; B4:C3 to C8 alkyl such as isopropyl, n-butyl, isobutyl, n-pentyl, 2-methylbutyl-(2), 2,4-dimethylpentyl-(2), 2,3-dimehylpentyl-(3), n-octyl, 2-ethylhexyl: phenalkyl of eight to ten carbon atoms such as 2-phenylethyl, l-methyl-3-phenylpropyl-(l), phenylethyl. alkoxyalkyl of a total of five to eight carbon atoms such as y-ethoxy- propyl. y-propoxypropyl and y-butoxypropyl; phenyl; phenyl bearing Ct to C4 alkyl, phenoxy. chloro and/or trifluoromethyl as a substituent or two substituents, such as 4-isopropylphenyl, 4-methylphenyl, 4-sec.-butylphenyl, 4-phenoxyphenyl, 4-chlorophenyl and 2-chloro-5-trifluoromethylphenyl.

Because of their outstanding technical and tinctorial properties, formulations of dyes of the following formulae (XI) and (XII)

in which K and M have the meanings given in the following Table are particularly preferred.

K x

-COCH3 ~CH (CH3 ) Cl ~0 F3 -CqH9(") 9H3 " ~C-CH2-CH(C-J3)2 CH3 -OH2-O1H-CH9 (n) 02H5 r ~CH2~CH2~O -OCH3 -CR (CH3) 2 CH3 '5 9-C2H5 CH3 'I -06H13(n) 85 OH EcH(c:3)j2 Br -CH(cH3)2 -SO -CI-I2-C-C4H9(n) 02H5 II (CH2)3-o-C2H5 (2,4- dimethylpentyl- (= 2,4- dimethyl- pentyl- (3)) K M ~~~

Dyes of the formulae (I), (VIII) and (IX) may from their constitution be denoted disperse dyes. They differ from vat dyes by their clearly better solubility in organic solvents.

A process is described however in German Patent 1,811,796 which makes possible the printing of water-insoluble dyes onto cellulose or cellulosic textile material. The statements made in this patent specification regarding the process conditions also hold good for the dye formulations according to this invention.

Further methods are described in German Laid-Open Applications DOS 25 24 243 and 25 28 743 according to which the dye formulations according to this invention may be applied. The printing methods are preferred.

There are obtained with the dye formulations according to this invention dyeings and prints having very good fastness properties of which especially wet fastness, fastness to crocking, resistance to dry cleaning and light fastness may be mentioned. In the case of prints there is no bleeding of any white areas.

In the following Examples, which illustrate the invention, parts and percentages are by weight unless stated otherwise.

Example I (a) Cotton cloth is printed by rotary film printing with a dye which consists of 10 parts of the dye of the formula:

in the form of a 30% formulation (see (c) below), 100 parts of polyethylene oxide of a molecular weight of 300 and 790 parts df all alginate thickening and the print is dried at 1000 . The print is then treated for one minute at 2000C with hot air, rinsed cold, soaped at the boil, again rinsed cold and dried.

A blue print which is fast to light and washing is obtained on a white ground.

(b) The dye used is prepared as follows: 51 parts of 1,4-diamino-2-acetylanthraquinone and 72 parts of 2-isopropylamino-4 phenyl-6-chloro-l ,3,5-triazine in 200 parts of o-dichlorobenzene are stirred for two hours at 1600C. After cooling the whole is suction filtered and the residue washed with methanol, with 14% aqueous ammonia and then with water. After drying 78 parts of a blue powder is obtained.

(c) The dye obtained according to (b) is converted as follows into an aqueous formulation: 30 parts of the dye l(b), 6 parts of lignin sulfonate and 10 parts of dipropylene glycol are stirred into 50 parts of water and the suspension is ground in a sand mill until the particle size is 0.5 micron or less. Then 1 part of pentachlorophenol is added and the content of dye is adjusted by the addition of water to 30% (based on the formulation). The formulation obtained is stable in storage.

When the dye specified above is replaced by an equal amount of one of the dyes specified in the following Table, dyeings are obtained having equally good fastness properties and the hues stated in the Table. Mixtures of the dyes given in the Table may also be used. The dyes are prepared analogously to Example l(b) and converted into formulations as described in Example l(c).

Ex. z1 z 2 z3 Hue

2 -CO-CH3 Zenyl -h'H-CH3 blue 3 1 -mlC2Hg tf 1 1 -CH2CH2CR, n 5 1 1 -H2CH2CH2CH " 6 r -!E.CH2CH-CR3 It CH3 r 1 -IIHCH2CH2CH2CI2CH3 n 8 -comr, cE3 -!.H^-CHo 3 3 3 9 1 " -h-.'.C-C3H2-CH ZS cl!3 CH3 10 1 -NHtCH217CH3 n 11 GnCH2CtHtCH2)3CH3 tt c5 It 1 -!CH2CH20X13 * 13 1 -;IHCIGcC202"5 II X 1 1 92C'I2CH20CH :2 Ex.Z1 Z2 Z3 Hue

its inert CH2CR rhenyl Ifrc -nrccrcrr,ac,gg blue 16 1 ~lSH(C112)30 tNg n 1 " I -Ccl!2)o(cn)4oH n 18 1 r -'HCH2CH20% N 1 1 -NHCH2CHOR " 1 w -NHCB2CR2t 11 21 1 N 1 1 -NH(CH2)50 (CH2)20 0 23 1 . -NECH2CH20O N 1 1 NH(CH2) W/C2S 1 1 -NN- I 1 1 N 27 w -O-C!3 is 1: 1 -B-O-C2z5 N 89 '&commat;1 N J 1 1 N 31 VCO CS3 w 3-C1 ,, 32 " -NH-P)-C1 N y 1 N CH3 Ex Z1 Z2 Z3 Hue

34 -N9 blue C02CH C02C4P -NH- II sCONHC2Y.5 36 1 -NH- II /CONHCqH9 37 1 - -NH- II .JiO2N(C2H5)2 02N~ 39 1 1 -NH-8 I' 1 1 " -(3 II 41 1 1 42 1 NC2H II C2H5 C:H3 1 - NcH CH CH3 CM 3 44 -CO-CH3 -O-C1 -NHC2HS 1l 45 " -NHCH2CH2CH3 II J16 -NH-CH ~ H3 CH3 47 .1 (CH2 ) 3CH3 II 48 -0-CH3 -NHCH2CH2CH3 n 49 1 1 )cflH3 cl!3 50 " 1 -NHCH2-Cy Is 51 ' ~0-OZH3 -NHCHs cl! Ex.Z1 Z2 Z3 Hue

52 -CO-CH3 -O-OCH3 -.Nh'Cii2CH2CR3 blue SO/(C05)2 53 1 4 -coc N 5s -zoc"g 1 N 56 -COCH3 phOrl -ph1 N 3 57 NE O F w N 58 1 -im- I, i, 5, 1 N NO2 60 1 N C3S 1 1 ' -NH 3 62 -NH--cH3 N CiR3 b-H3 63 -COCH3 pherl -NS) cl!3 MCo-CaH17 < r.$ 9-coUrg caHlT n 65 " 1 -Nrr-CY2-cq2-ct n Example 66 (a) A union fabric of polyester and cotton in the ratio by weight 67::33 is printed with a paste consisting of 20 parts of the dye of the formula:

in the form of an aqueous formulation prepared according to (c) below, 120 parts of the reaction product of polyethylene oxide of a molecular weight of 300 with boric acid in a molar ratio 3:1 and 860 parts of a 10% alginate thickening. The print is dried at 105"C and treated for six minutes with superheated steam at 180"C. It is then first rinsed with cold water, soaped at sOOC, rinsed cold and dried. A blue print which is fast to light and washing is obtained on a white ground.

(b) The compound specified in 66(a) is prepared as follows: 7.6 parts of 1,4 diamino-2-(2',4',6'-trimethylbenzoyl)-anthraquinone and 5.5 parts of 2-isopropyl amino-4-phenyl-6-chloro-l,3,5-triazine in 80 parts of o-dichlorobenzene are stirred for three hours at 180"C. After cooling the whole is diluted with 40 parts of cyclohexane, suction filtered and the product washed with methanol and dried. 11.9 parts of a blue powder is obtained.

(c) The powder is converted into an aqueous formulation as described in Example l(c).

When the dye in the paste is replaced by one of the dyes in the following Table dyeings with similar fastness properties are obtained in the hues given in the Table.

The dyes specified in the Table are prepared by methods analogous to that in Example 66(b).

Ex. 2 P Hue .

67 -CO-O -Cy -Ni-CH/Cb blue Es -NH-CKce; blue -i-AcHc ri U U tt To co--cl!3 70 -co-CH, 71 w r -h-dCH2CH2CCE13 n 72 " -h'H-O :1 73 ~O~OCH3 -2.rdCHo 3 1 74 ~Cow C$; n -llStCR2)3o-H3 CJ 75 U U -'.mCcP)3c3 II 76 U U II 77 -Co- < 3-OCE3 - - Ca3 II cH 3 78 - Crf3 79 " " -lad(cH2)cH3 n 80 U I -I 81 " r -f.?lCH2CH2CH20C2iS n 82 U Ir 83 " cl!3 3 -N-dCHo 3 n ca3 Ca3 Ex.Z Z Z Hue

84 -co\c-/\ -O IEC;; OCH3 blue 3 85 w -'...(c2)3oc2'r.5 'I 86 w w -?.H- C9 87 " IC ~p31L.BIC$CH3 ---Cils 88 -cooca3 -O SCH3 3 Ir 89 " C-;;2)3CR3 90 -COOCB/CH3 w WCP3 Ir ----Ci's Ci3 91 p w -I.HCRC-O -ts 92 P3 - II 3 3 93 p - (C".2)3CH3 n 94 -}t 2 U 95 -i'o2 - -',!9.CH2cH2CCH3 II -NR- n 97 -CN -O -NHCHZ N 98 " I NH(C)3OC5 n 99 1 -(3-CH3 ~}*CRtCH3)2 n 100 " Sd- II ,CH3 101 -CO2CR3 t F.CHCR n 102 -502 O -NBC.; CR CU 3 103 p - -ifltCca)3oc5 II 10b p n Ex. zl z2 z3 Hue

105 -S02-O-CH3 HCH2CH2cu3 blue 106 " " -2.'HCH2CHZ- Ir L-J 107 -SO2 --Cci's iHg 108 -OCH3 - ,I CS 109 Cci's t -21H(Cll2)3QC2R5 S.

110 " -O-OCH3 - :CH2CY.2CH2CH3 II Example 111 (a) Cotton cloth is printed by roller printing with a print paste consisting of 15 parts of the dye of the formula:

in the form of a 30 /O aqueous formulation, 110 parts of polyethylene oxide of a molecular weight of 350, 30 parts of the diethanolamide of oleic acid and 845 parts of a 10% alginate thickening. The print is dried at 100"C and then fixed by a treatment with hot air at 1950C for one minute. The print is finished off as described in Example 1. A fast red print on a white ground is obtained.

(b) The dye specified in Example 111(a) is prepared as follows: 12 parts of 1amino4-hydroxyanthraquinone and 13.5 parts of 2-isopropylamino-4-phenyl-6chloro-1,3,5-triazine in 100 parts of o-dichlorobenzene are stirred for two hours at 1 700C. After the whole has been cooled and diluted with a small amount of methanol it is suction filtered. The product is washed with methanol and dilute aqueous ammonia and dried. 18 parts of a red powder is obtained.

(c) The dye is converted as described in Example l(c) into an aqueous formulation.

When the dye specified in Example 111(a) is replaced by an equal amount of one of the dyes specified in the following Table dyeings having similar fastness proPerties are obtained in the hues specified in the Table. The dyes are prepared analogously to Example 111(b).

Ex. Z4 Z2 Z3 Hue

,ca, 112 H 43 -0 yellow 113 H -C 18 114 H - 4iu Isr;crc3 '1 115 H r ,'iiC2i's N 116 H C52CE2- < 9 117 H r, u 118 8 --acs, -lE.CI 119 H Q-CR) -}ECEE CE3 Ir 120 OH ~NZC2RS red 121 OH r 'CB 122 OH -0nEXCE2)3 C2B5 N 123 OR aS CHaCg3 I CH3 124 OH O -NHCH2 125 CM w NH z II 126 OH II 127 CM -iH--r II 128 OH -O-OCH3 ~SHCHZ !NcHH 3 EX.Z Z2 Zzi iT.ue Ex. Z4 Z2 Z3 Hue

129 OH -N -CH3 - C red red 130 "Ci\c/ H CH3 blue 131 w -CH3 R 132 w n{CH2CH2 < 9 133 -Enr-0CHJ -JH- < CH3 134 2 -NH2 I7 CH3 135 71 w 136 --cf{3 -NFCH(CH3)2 11 137 . -NHCH2CH20CH " 136 -NHCH3 - II -'-'ci's 139 " - -(ch2)3CH3 I' 140 iu- - NNCH II ci's 141 -- - -ica2CN2 " 12 8 -NH(CH2)30CH3 II 143 -NH- O -CH3 " CEX3 ----Ci's 4 - - -NN(CN2)30CH3 145 w --cH3 -WHCH CH 11 NHCH. I 146 7. -O-OCH3 " 11 rh /CH, CH3 ----ci's $8 -NH(CH2)3CH3 Ex. z4 z2 z3 Hue

149 I -O-CH3 -^4HCH2CH2CH3 blue 150 w -NHCH2CH2CH20CH3 151 - O CH3 -NHCH II 3 152 -NHCOCH3 t red Ca 153 153 -NHCO-C-CH3 17 CH3 154 -NNCO- O 7 155 -NHCO-rS-CHI 156 -NHCO- O -OCOCH3 ~ O n n 157 -S- - cH3 II N}ICHCH3 158 71 -NHCH2CH2- O tí 159 - O -OCH3 -NHCH2CH20CH3 fl 160 - --cH3 HHC. H -Ci's II Ca3 161 -Br - -NHCH;CH3 yellow Ca3 162 -Cl - 163 -OCH - - orange 3 orange 164 - -NtICH2CH2-.C O lí 165 -NH- O -OCH3 ~ --o5a11(n) blue 166 71 -NN- p n couch 3 167 - - -'m-c5 n 168 " " NH(Ca2)30C2i's 18 169 z r " Erl-(CH2)3~0cR fl Ex. z4 z2 z3 Hue

170 " - -Nt o-C.a2Cu.2-t,3 blue 171 " IoCiI2-dy CI:: '3 172 w " -btH-C-C2H5 Ir CH3 173 r , ~l-CH(-CP{CH3)2)2 N 174 " " Cn- (CH23~0~Cff2~CH~C4Rg(n)wn-(C.'12'-0-C2-CH-C4i's(n) Ir CHs 175 - - H2-CH-C4R9(n} Ir C2H5 Example 176 (a) Union cloth of polyester and cellulose in the ratio by weight 67:33 is screen printed with a dye formulation consisting of 30 parts of the dye of the formula:

in the form of the formulation obtained according to (c) below. 100 parts of the reaction product of polyethylene oxide of molecular weight 300 with boric acid in a molar ratio of 3: 1, 30 parts of the diethanolamide of oleic acid and 840 parts of a 30o alginate thickening and the print is dried at 1100C. It is then treated for five minutes at 185 C with superheated steam and finished off as described in Example I. A fast blue print on a white ground is obtained.

(b) The dye used in Example 176(a) is prepared as follows: 7 parts of the compound:

120 parts of N-methylpyrrolidone and 5 parts of phenyldichloro-l.3.5-triazine are stirred for two hours at 70" to 80"C. 1,2 parts of isopropylamine is then added and the whole is stirred for another three hours at 8() C. The reaction mixture is suction filtered, the filtrate is diluted with water, the precipitate is suction filtered and dried. 7 parts of a blue dye powder is obtained.

(c) The dye is converted into an aqueous formulation as descnbed in Example l(c).

When one of the dyes specified in the following Table is used instead of the dye specified in Example 176 dyeings having similar fastness properties are obtained which have the hues set out in the Table. The dyes are prepared analogously to Example 176(b).

Ex. z1 z3 z2 Hue

177 ,CH,blue - blue 278 " -IIH'CH)JOC2H5 - II 273 Ca3 II (C-Y2)30- O Ci's lso - -NHw 181 ss O t (CB2)50- O CH3 tt n CH3 182 " -03HCH2CH2CH3 " 11 J-N CH3 183 at H2CH20 b C1 -; ;HcH a3 18 " -NHC4Hg " II 185 A CB2 g O -NX-CB(CH3)2 " 11 les 286 CH20- b -C1 -NHCH N II 187 - -NHCH2 t t tX 288 -',-0H3 ' 7t rCH2)O O CH3 \ CH3 leg " -NH- O " Nl 15v / O t - CH3 O Ni's - II 191 " -13B(CH2)3oCH3 - II 192 Ak -NHCH / II NHCH;CH;; 293 zCH2 t n II 7. zI 7 ix zl ?) 2

294 / S t " n blue SCH) N -N 195 --c:r3 Ci's 196 at C4H9 197 n z ~ O --OCH3 Example 198 (a) Cotton cloth is padded on a padding machine uith a Ijqunr containing ' parts of the dye of the formula:

in the form of an aqueous formulation obtained according to (c) below, 300 parts of a 3 Ó alginate thickening, 550 parts of water and 130 parts of polyethylene oxide having a molecular weight of 300. Liquor pickup is 800o based on the cloth. The cloth is dried at 1000C.To fix the dye it is treated for five minutes with superheated steam at 1900C. It is then rinsed cold, washed at 900C in a liquor containing 3 parts of the condensation product of a mixture of C12 to C15 alcohols with ethylene oxide to 997 parts of water.

When a polyester/cotton union fabric (weight ratio 67:338 is used instead of a cotton cloth, a blue dyeing in which the two fibers are dyed the same shade is obtained after fixing. Instead of fixing with superheated steam fixing may also be carried out with hot air in two minutes at 195 C.

(b) The dye used in Example 198(a) is prepared in the following manner: 27.9 parts of 4,8-diaminoanthrarufin, 23 parts of phenyldichlorotriazine and 200 parts of N-methylpyrrolidone are stirred for two hours at 800 C. 20 parts of y-methoxypropylamine is then dripped in and the whole is stirred for another three hours at 800C. The whole is then cooled, poured into water, filtered and the filter cake is dried. 30 parts of a blue powder is obtained.

(c) The powder obtained according to (b) is converted as described in Example l(c) into an aqueous formulation.

By using an equal amount of a dye specified in the following Table instead of the dye specified in Example 198(a), a dyeing with similar fastness properties are obtained. The hues of the dyeings are given in the Table. The dyes may be prepared as described in Example 198(b) and converted into aqueous formulations according to Example l(c).

Ex. Z4 Z5 Z6 Z3 Hue

299 OH NH2 OH -NHCCH3 blue 200 " H3 ----ci's fi CH3 201 w - -NHC4H9 202 - - ~NHCH2CH2CH2OC3H7 II 203 w - -JHCH,CH,oCH,CH20CH, -NHCH2CH2oCH2CH2OCH3 2o - w II 2 - dCH2CH2-n 206 w NHCH2CH2OCIX2CH2 II 207 w -NH-e) 208 w w -NH- < -CH3 l ,O9 w w w -NH- < -OCH3 II 210 " OH CHp 211 b w -NHCH2CH2CH2CH II 212 w -NHCH2CH20CN2CH20-O n 213 w - -NH- < CH3 12 21 H- < each, 215 w - - II 216 w w -O- < Ex.ZX Z5 Z6 Z3 Hue

i.r-,,CH3 OH ON ----Ca3 blue 218 w w -NHZF:2CH2CH2OCH3 II 229 w -U?IH2CH2-- " -NHCH2CH2 X20 w NH2 fi ~NHCH2CH2OCH2CH2Q II 221 " w -UHW I(11 222 " -Nd-O-OCH2-C) II w 3 " " Ca 224 " NE{2 -SHZH CH 11 Ca3 2 " -lr CH2CR2CH20C2H5 226 " " -NH--Ca3 227 -NH-4 OCH2- < 228 or OH N 2 -NHCH 3 N}{Ca----Ca3 229 - - -NH-CB3 II "0 " " " -NH- < II 231 w " " -NH- < -O- < 232 w N02 Ca -}IHC4H9 233 ~NHCH2CII2CH2OC2H5 234 " w -NH- < OC2H5 IG 235 OH N 2 OH 236 w w NH- < (I 237 -NHCHCH2CH3 " -NHCH H3 CH3 - - CH3 11 cl!3 CH3 Ex. z4 Z5 z6 z3 Hue

238 " - - -Nil- -OCi's blue 239 w w w -NH- -OCH2- II OH 08 NH-O " NHC8/CH3 350 OH 242 - - - -NHC4H9 II 242 w - - -NH-O-CH3 243 " - -N8-CY OC2 5 244 w OH N8-O NHZH/CH3 "11 5/ CH3 245 - - - NH-O-CH3 II 6 NH2 H SC83 violet CH3 2*7 w H -CH2CH2CH20C285 28 " " H -N8-O C2H5 2X9 " ft H iH--OC- .1 2SO w 2 H H CH blue To 251 " w NO2 w II 252 " " w -NH-(3-CH3 253 H OH H ca3 'iiiCaca3 yellow 255 H NN2 H " orange 255 H w H -NH-(3-CH3 II 256 R " H NHCH2CH2 O Ex. zl Z5 z6 z3 Hue

NHCHCa3 ~~ H -NHC0 H yellow ca3 258 H w H -NHCH2CH2Cli20CH3 II 259 H - NHCOCH3 H -NHCHz 3 - ca3 p H H NH2 " orange 261 H H " -NH--CH3 II 262 H -NHCHo H5 H ./CH ii -'--ca 5 CH3 263 oH H H OH2 yellow 264 w -liH-C) CH3 OH n blue 265 t r C;;Hg(n) II 266 OH -NH2 -N82 C tCH3)3 II 267 " w -C5Nll (n) n 268 - I -c,CH3)2-c2il5 'I 269 * 269 - S r .0H2-c,.ci's OH 270 w w C6%(n7 271 -OH -OH -nH2 -OH2-CH -C4il9tn) C2H5 n2 - - - -CHt-CHv ) n -'--cH32 273 | CB273-oCH2-CH-C4Hg n) n c2H5 nx I 5 1 (cN2)3-ocH3 N 275 " - -(CH2)3-oc2g5 276 " w -(CH2)TOCJK7ln) m " I - H2)3-OC4ff9Cn) tCH2)2 OC3H7 ( 279 " - - 3-OCH2-O-C1 n Ex. Z4 z5 z6 z7 Hue

'so I I -Ta-ocH2''i9 blue X - --OCH2- t 262 -O- {CH272 0 263 -OH ZIJH2 -OH O0CH2-O tt ,t 261' I - C(CH3)3 n w - - -C(CH)2'C2!5 - c4CH352-CS5 II 286 " t - cit2-c,-cIt3 OH II 20,,' " X -CsH1(") I c6H3() 268 -OH -NH2 -OH -CHZSiI-CI;H9!n) c2ii5 269 - . I CH~cgg 2 290 w CH273-O-CH2-CA-CH9tn7 II C2H5 291 " I -0~oCN2-C > -cl n 292 - OCiR b w I I OCCH2)2{) H Example 294 (a) Cotton cloth is padded on a padding machine with a liquor consisting of 150 parts of polyethylene oxide in 850 parts of water so that the liquor pickup is 80% and the padded cloth is dried at 1000C. The cloth pretreated in this way is printed with a rotary screen printing machine with a dye formulation which consists of 30 parts of the dye bf the formula:

in the form of the aqueous formulation obtained according to (c) and 970 parts of a 10% alginate thickening.After drying the print at 1050C it is treated for seven minutes at 1850C with superheated steam at 185 C and finished off by rinsing and soaping as described in Example 1. A fast yellow print is obtained on a white ground.

(b) The dye is prepared as described in Example 111(b), an equimolar amount of C-phenyl-4-amino-(1,9)-anthrapyrimidine being used instead of l-amino-4- hydroxyanthraquinone.

(c) The dye obtained is converted into an aqueous formulation as described in Example l(c).

When the dye specified in Example 294 is replaced by one of the dyes specified in the following Table dyeings are obtained with similar fastness properties in the hues stated. The dyes are prepared analogously to the statements in Example 111(b) and converted into aqueous formulations according to Example 294(c).

Ex. z1 z2 z3 Hue

'95 -Q -1MCHCHCff20CzH5 yellow 296 1 II XH-O- x2 O 298 cH3 II 299 H /ca, -WRCR\CH, n 300 H :Iic4 II

Ex.Z4 Z5 Z6 Z3 Hue

301 Ii -JIHCB2CH20CS2CH2 O yell ow 302 H -NH-(3-CH3 303 cil -NHCH- 1111 3 CH3 Cii3 3011 -O-CH3 n 305 -(3-C1 306 OH ff II t 'Os t '#H'-OCH2,I 39 " 3 -NHCHv ./CR,II CH3 Ex. z2 z2 z3 Hue

310 - 3 red CH3 311 -=R2CH20CH3 II > 2 3 N > 3 ',IN.-Oci2 t 314 ~-CN3 ,-q-cBj 3 Example 315 (a) Cotton cloth is printed by rotary screen printing with a dye formulation which contains 10 parts of the dye of the formula::

in the form of an aqueous formulation obtained according to (c), 100 parts of polyethylene oxide of molecular weight 300 and 790 parts of a 3% alginate thickening and the print is dried at 100"C. It is then treated for one minute at 2000C with hot air. The print is rinsed cold, soaped at the boil, again rinsed cold and dried.

A blue print on a white ground is obtained; it is fast to light and washing.

(b) The dye is prepared analogously to Example l(b) by reaction of I mole of 1 ,4-diaminoanthraquinone with 2 moles of the appropriate triazine derivative.

(c) The dye is converted into an aqueous formulation as described in Example let).

When one of the dyes specified in the following Table is used instead of the dye specified in Example 315, dyeings are obtained having similar fastness properties and the hues given in the Table.

Example z2 z3 Hue

6 - X*Hg ore 317' -IJHCH2C82CH20CH3 orange 318 " -NN:H2CH2-t9 orate 319 -1ECS2CH2R2t O orange 320 O 3 orgnge 312 -Cii3 H3 orange -N?H3 312 U -iH orange 323 -O-OCH3 -NHCH/3 or nge -O-OCH3 -iH%) orange 325 1 oCH2 0 orange Example 326 (a) Cotton cloth is printed by rotary screen printing with a dye formulation containing 10 parts of the dye of the formula::

in the form of a 30% aqueous formulation (see (c)) and 100 parts of polyethylene oxide (molecular weight 300) in 790 parts of a 3 < , alginate thickening and the print is dried at 100 C. The printed cloth is then heated for one minute with hot air to 2000C, rinsed cold, soaped at the boil, again rinsed cold and dried.

A blue print on a white ground is obtained.

(b) The dye used is prepared from 1,4-diamino-2-phenylsulfonylanthraquinone by reaction with 2-(2'-ethylenehexylamino)-4-phenyl-6-chlorotriazine as described in Example 1(b).

(c) The dye obtained according to (b) is converted as described in Example l(c) into a 30% aqueous formulation. A liquid formulation is obtained which is stable in storage.

When the dye of Example 326(a) is replaced by the same amount of one of the dyes specified in the following Table dyeings having similar to equal fastness properties are obtained. The hues of the dyeings are given in the right-hand column. Mixtures of two or more than two of the said dyes may also be used.

The dyes are prepared as described in Example l(b) or 326(b) and converted into liquid formulations as described in Example l(c).

Ex. z1 z2 z3 Hue

32" -llO2-O H (CR3)2 0CH3 blue 3a8 C5Hll(n) N 3 =-C,R9(n} n ) * C - z z (CH2)2t " cH3 33S H2{) ta 331 -NN-O-CEI(CI}3)2 D3 1 -11H-C3R7 tn) N 334 1 1 -MH--O N 335 1 -NR-C2R5 N S Ih-(CH2)2t II w w ~t-CF Ex. z1 z2 z3 Hue

336 1 1 -HH- tCH2)3-0-(C82)2-Oe blue > (3-eg3 n )40 -HH-n C2'ii5 341 - -Br N H3v 342 N ::-3 II -WH-rJ J 343 -ssO2-O-C}X3 t -NH-cH2-H-c;Hg(n) N 344 1 .MK (CH2)3-0 N 345 -NH-eCH-tCH2)2 II CN3 344: 1 1 iG\O/\ N 3uke7 1 r -2E-O-CH(CH3)2 n -NH-O-Ot Example 349 (a) Union fabric of polyester and cotton in the ratio by weight 67:3A is printed with a paste consisting of 10 parts of the dye of the formula:

in the form of an aqueous formulation prepared according to (c) below. 110 parts of the reaction product of polyethylene oxide of the molecular weight 300 with boric acid in the molar ratio 3:1 and 790 parts of a 10% alginate thickening.The print is dried at 1050C and treated for six minutes at 1800C with superheated steam. It is then rinsed with cold water, soaped at 800 C. rinsed again cold and dried.

A blue print fast to light and washing is obtained on a white ground.

(b) The compound specified in Example 349(a) is obtained by the reaction of 1,4-diamino-2-methoxyanthraquinone with 2-isopropvlamino-4-( l'-methoxs- phenyl)-6-chloro-1,3,5-triazine in o-dichlorobenzene for three hours at 1800C. After the reaction mixture has cooled it is diluted with cyclohexane. and the dye is suction filtered, washed with methanol and dried. A blue powder is obtained.

(c) The powder is converted as described in Example l(c) into an aqueous formulation.

When the said dye in the paste is replaced by the same amount of one of the dyes set out in the following Table dyeings are obtained having similar fastness properties and the hues given in the Table.

Ex. z1 z 2 z3 Hue

eli SO -OCR3 blue .3 CH3 CH3 351 1 --c6H13Cn) I, 352 1 S -CHc-cH(CH3)2) II 353 354 I S II 355 1 S II 3 (cH2)2 m S blue 358 " -1t--o (cii2)2 359 S -NN-O-OCN2-0 II 360 " -tlN-(CN2)3-o-CN2-CE-C4X9tn lf C2X5 361 S tE-CN2-CgN-C4Rgtn) * C2Ns 362 S 3 -tqH-tCH2)3-CC2le5 363 S -t4z-c5Hll (n) ss t-C2N5 l l 365 -tSN-C4Ngtn) Example 366 (a) Cotton cloth is printed by roller printing with a print paste consisting of 15 parts of the dye of the formula:

in the form of a 30 Ó aqueous formulation, 110 parts of polyethylene oxide of the molecular weight 350, 30 parts of the diethanolamide of oleic acid and 845 parts of a 10% alginate thickening. The print is dried at 100 C and then fixed by a treatment with hot air at 1950C for one minute. The print is finished off as described in Example 1. A fast blue print is obtained on a white ground.

(b) The dye specified in Example 366(a) is prepared by the reaction of 1.4diamino-2-bromoanthraquinone with 2-isopropylamino-4-phenyl-6-chloro- 1.3.5- triazine analogously to Example Ill(b).

(c) The dye obtained is converted as described in Example l(c) into an aqueous formulation. A very finely particled formulation is obtained which is stable in storage.

When the dye specified in Example 366(a) is replaced by one or more of the dyes specified in the following Table dyeings having equal to similar fastness properties are obtained.

The dyes are prepared as described in Example 366(by and converted into aqueous formulations as described in Example l(c).

Example z Hue

3Sr * c2S5- blue 368 -ua-c(n) n 369 -}-C5Bll tn) 3,0 -D{oCtH3)3 II CH3 391 .RHc1-c2H5 0.3 Na uf-cr-r-cW N CR15 N -IIR-tCR2)2 e ) 3,4 -tH-tCH2)2- n CH3 3,5 ^ CH2 ,CH O CR 3 376 -X}-tCH2)3-O-tR2)2 " 3t7 4-(S2)2- -S3 tit 378 rtCR2)3-tC2R5 tit 3,9 .iR-cH2-C1 H n OH 3Ba-OCK3I 301 n 382 MM-O- II 383 ~t~(3~Cb tt gX -0-c2R5 tit WHAT WE CLAIM IS:--- I. A dye formulation for dyeing or printing cellulose or cellulosic fibrous material which contains, in addition to one or more dispersing agents and water retention agents and water, one or more dyes devoid of sulfonic acid groups and having the general formula:

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (21)

1. **WARNING** start of CLMS field may overlap end of DESC **.

   Example z Hue

   3Sr * c2S5- blue 368 -ua-c(n) n 369 -}-C5Bll tn) 3,0 -D{oCtH3)3 II CH3 391 .RHc1-c2H5 0.3 Na uf-cr-r-cW N CR15 N -IIR-tCR2)2 e ) 3,4 -tH-tCH2)2- n CH3 3,5 ^ CH2 ,CH O CR 3 376 -X}-tCH2)3-O-tR2)2 " 3t7 4-(S2)2- -S3 tit 378 rtCR2)3-tC2R5 tit 3,9 .iR-cH2-C1 H n OH 3Ba-OCK3I 301 n 382 MM-O- II 383 ~t~(3~Cb tt gX -0-c2R5 tit WHAT WE CLAIM IS:--- I.A dye formulation for dyeing or printing cellulose or cellulosic fibrous material which contains, in addition to one or more dispersing agents and water retention agents and water, one or more dyes devoid of sulfonic acid groups and having the general formula:

   in which A is unsubstituted or substituted anthraquinonyl anthrapyridone or anthrapyrimidine; X is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical; B is hydrogen or an aliphatic radical; B' is an aliphatic, cycloaliphatic, araliphatic or aromatic radical; or the group BN-lB1 is a saturated five-membered, six-membered or seven-membered heterocyclic radical; and n is 1 or 2.
2. 2. A dye formulation as claimed in claim I which contains in addition to a dispersing agent, a water retention agent and water a dye of the general formula given in claim 1 in which n is 1 or 2; A is (I) a monovalent or divalent a-anthraquinonyl radical which (a) optionally contains as a substituent in one or more further a-positions: hydroxy; C, to C4 alkoxy; amino; C1 to C8 alkylamino; C, to C8 alkylamino substituted by hydroxy, C1 to C4 alkoxy, cyano or carbonylalkoxy of one to five carbon atoms; phenylamino; phenylamino substituted by C, to C5 alkyl, methoxy, ethoxy, phenoxy, chloro or bromo;C1 to Ce alkylthio; phenylthio; phenylthio substituted by C1 to C5 alkyl;

   in which R' is C, to C5 alkyl, phenyl, or phenyl substituted by C1 to C4 alkyl, bromo, chloro, methoxy or ethoxy; and in the case of more than one substituent these may be identical or different; and (b) optionally contains in one or more ,B-positions as a substituent: chloro, bromo, methyl, ethyl, C, to C6 alkoxy. phenoxy, alkylphenoxy, of one to six carbon atoms in the alkyl, chlorophenoxy, bromophenoxy, C, to C6 alkylthio, phenylthio, alkylphenylthio of one to six carbon atoms in the alkyl, acetyl, propionyl, benzoyl, monomethylbenzo'l,dimethylbenzoyl, trimethylbenzoyl, phenoxybenzoyl, C, to C8 alkoxycarbonyl,-alkylaminocarbonyl or N,Ndialkylaminocarbonyl of one to six carbon atoms in each alkyl, phenylaminocarbonyl, alkylphenylaminocarbonyl of one to six carbon atoms in the alkyl, cyano, C, to C6 alkylsulfonyl, phenylsulfonyl, C1 to C6 alkylphenylsulfonyl, N-alkylsulfamoyl or N,N-dialkylsulfamoyl of one to six carbon atoms in each alkyl.Nalkoxyalkylsulfamoyl or N,N-bis-alkoxyalkylsulfamoyl of three to twelve carbon atoms per alkoxyalkyl, and wherein in one of the a-positions or B-positions a nitro group may be present or in one opposition an oxadiazole or thiodiazole radical may be present and the number of substituents in all may be up to six, or (2) an anthrapyridone or anthrapyrimidine radical, these radicals optionally bearing C, to C6 alkyl, hydroxy, amino,

   in which R' is as defined under (a) above, phenyl, C, to C5 alkylphenyl. benzoyl or cyano, the number of the substituents being zero, one or two: X is hydrogen; linear or branched C, to Ce alkyl;C, to C6 alkyl bearing chloro, bromo C, to C alkoxy, alkoxycarbonyl of a total of two to five carbon atoms, C, to C4 alkylsulfonyt and/or phenoxy as substituents; cyclohexyl; phenalkyl of seven to ten carbon atoms; phenyl or naphthyl; phenyl or naphthyl bearing C, to C16 alkyl, C, to C4 alkoxy, C2 to C4 hydroxyalkoxy, C, to C4 alkylthio, chloro, bromo, trifluoromethyl, nitro, cyano, sulfamoyl, N-alkylsulfamoyl or N,N-dialkylsulfamoyl of one to eight carbon atoms per alkyl. carbamoyl, N-alkylaminocarbonyl or N,N-dialkylaminocarbonyl of one to eight carbon atoms per alkyl, carbonylalkoxy of a total of two to five carbon atoms, C, to C4 alkylsulfonyl or C1 to C4 alkylcarbonyl as substituents; the number of substituents on the phenyl or naphthyl being one to three and the substituents being identical or different: B is hydrogen; linear or branched C1 to CA alkyl; C, to C4 alkyl bearing hydroxy.

   cyano, chloro, bromo, carbonylalkoxy of a total of 2 to 5 carbon atoms, N-alkylaminocarbonyl or N,N-dialkylaminocarbonyl of one to eight carbon atoms per alkyl. C, to C4 alkylsulfonyl or phenoxy as substituents; or alkoxyalkyl of a total of three to six carbon atoms; and B' is (a) unsaturated or saturated, linear or branched C, to C,8 alkyl; (b) C2 to C6 alkyl substituted by hydroxyl, cyano, chloro, bromo, carbonylalkoxy of a total of two to five carbon atoms, N-alkylaminocarbonyl or N,N-dialkylaminocarbonyl of one to eight carbon atoms per alkyl, C1 to C4 alkylsulfonyl, dialkylamino of one to four carbon atoms per alkyl or phenoxy, the number of substituents being 2 or I and the two substituents if present being identical or different; (c) alkoxyalkyl of a total of three to eleven carbon atoms; (d) hydroxyalkoxyalkyl of a total of four to ten carbon atoms; (e) phenoxyalkoxyalkyl of a total of ten to twelve carbon atoms; (f) saturated five-membered, six-membered, seven-membered or eight-membered cycloalkyl or polycycloalkyl;; (g) cycloalkyl optionally bearing one to three identical or different substituents selected from C, to C6 alkyl, cycloalkyl and hydroxyl; (h) phenalkyl of a total of seven to ten carbon atoms in which the alkyl radical may be substituted by hydroxy and the phenyl radical may be substituted by C, to C16 alkyl; or (i) phenyl of naphthyl in which one to three hydrogen atoms may be replaced by C, to C,8 alkyl, chloro, bromo, trifluoromethyl, nitro, cyano, C, to C5 alkoxy, C, to C4 alkylthio, sulfamoyl, N-alkylsulfamoyl or N,N-dialkylsulfamoyl of one to eight carbon atoms per alkyl, N-phenylsulfamoyl, carbamoyl, N-alkylaminocarbonyl or N,N-dialkylaminocarbonyl of one to eight carbon atoms per alkyl, carbonylalkoxy of a total ot two to six carbon atoms, C1 to C4 alkylsulfonyl, phenylsulfonyl which may bear alkyl as a substituent in the phenyl, C1 to C4 alkylcarbonyl, phenalkoxy of seven to ten carbon atoms wherein the phenyl radical may bear chloro, bromo or cyano as a substituent, phenoxy or 4-chlorophenoxy, wherein the substituents may be identical or different and in the case of more than one alkyl or alkoxy or alkyl and alkoxy the sum of the carbon atoms in these substituents is 12 as a maximum.
3. 3. A dye formulation for dyeing and printing cellulose or cellulosic fibrous naterial containing in addition to an anionic or nonionic dispersing agent, a water retention agent, a disinfectant and water a dye of the general formula:

   in which A3 is a radical of the formula:

   in which hal is chloro or bromo: m is zero, I or 2: R' is hydrogen, chloro, bromo, methyl, ethyl, C, to C6 alkoxy, phenoxy. alkylphenoxy of one to six carbon atoms in the alkyl. chlorophenoxy. bromophenoxy. C, to C6 alkylthio, phenylthio. alkylphenylthio of one to six carbon atoms in the alkyl.

   acetyl, propionyl, benzoyl, monomethylbenzoyi. dimethylbenzoyl. trimethyl- benzoyl, phenoxybenzoyl, Ct to C alk oxycarbonyl, N-alkylaminocarbonyl or N.Ndialkylaminocarbonyl of one to six carbon atoms per alkyl, phenylaminocarbonyl, alkylphenylaminocarbonyl of one to six carbon atoms in the alkyl, cyano. nitro, C, to C6 alkylsulfonyl, phenylsulfonyl, C, to C8 alkylphenylsulfonyl, N-alkylsulfamoyl or N,N-dialkylsulfamoyl of one to six carbon atoms per alkyl, N-alkoxyalkylsulfamoyl or N,N-bis-alkoxyalkylsulfamoyl of three to twelve carbon atoms per alkoxyalkyl; R2 is hydrogen, hydroxy, C1 to C4 alkoxy, amino, C, to C6 alkylamino;C1 to C8 alkylamino substituted by hydroxy, C1 to C4 alkoxy, cyano or carbonylalkoxy of one to five carbon atoms; phenylamino; phenylamino substituted by C1 to C5 alkyl, methoxy, ethoxy, phenoxy, chloro or bromo; C1 to C6 alkylthio; phenylthio substituted by Ct to C5 alkyl;

   in which R12 is a saturated, linear or branched C: to C5 alkyl: phenyl; phenyl substituted by C, to C4 alkyl, bromo, chloro, methoxy or ethoxy; R3 and R4 are hydrogen, hydroxy, C, to C4 alkoxy, linear or branched C, to C4 alkylamino,

   in which R12 has the above meanings and the radicals R3 and R4 may be identical or different: R6 is hydrogen or methoxy; R6 is nitro or the groups specified for R7, R7 and R6 then being identical or different; R7 is hydrogen, hydroxy, saturated linear or branched C, to C5 alkylamino and the alkyl may be substituted by C1 to C4 alkoxy, hydroxy or cyano; R6 is C1 to C5 alkylamino or hydroxy: R6 is phenyl; phenyl substituted by C1 to C6 alkyl, C, to C4 alkoxy, chloro or bromo: C1 to C,O alkyl in which one or two hydrogen atoms are replaced by chloro, bromo, hydroxy, cyano, Ct to C4 alkoxy, dialkylamino of one to four carbon atoms per alkyl, carbamoyl, carbonylalkoxy of a total of two to nine carbon atoms, C1 to C5 alkylthio, phenyl or phenoxy, and in which in the phenyl substituents one or two hydrogen atoms may be replaced by chloro, bromo, C, to C4 alkyl, methoxy, ethoxy. alkoxycarbonyl, alkylthio. alkylsulfonyl and/or N-alkylsulfamoyl of one to four carbon atoms per alkyl; C1 to C5 alkylthio;C, to C,0 phenylalkylthio; phenyl thio: phenylthio substituted by chloro, bromo. Ct to C4 alkyl. methoxy or ethoxy; R'O is phenyl; C, to C5 alkyl: C, to C6 alkylthio: C3 to C6 alkoxyalkyl; C1 to C5 alkylamino: methoxy: ethoxy: phenalkylthio of one to five carbon atoms in the alkyl; R" is amino or C1 to C5 alkylamino; R'3 is hydrogen; C1 to C6 alkoxycarbonyl; C, to C4 alkylcarbonyl: benzoyl or cyano: R'5 is hydrogen; C1 to C5 alkyl; or phenyl; R'4 is hydrogen: C1 to C5 alkyl; phenyl; or C1 to C5 alkylphenyl: and X, B, B' and n have the meanings given in claim 2.
4. 4. A dye formulation as claimed in claim 3 in which R' is hydrogen, bromo.

   chloro, acetyl, carbonylalkoxy of one to five carbon atoms in the alkyl, benzoyl.

   monomethylbenzoyl, dimethylbenzoyl, trimethylbenzoyl, methoxybenzoyl. ethoxvbenzoyl, phenoxybenzoyl, N-alkylaminocarbonyl of one to four carbon atoms in the alkyl, nitro, cyano, C, to C4 alkylsulfonyl, phenylsulfonyl, methylphenylsulfonyl or C, to C4 alkoxy: R2 is hydrogen, hydroxy, amino, C, to C4 alkylamino; phenylamino, phenylamino substituted by C1 to C5 alkyl, methoxy, ethoxy or C2 to C4 C-acyloxy; or C, to C4 alkoxy; R3 and R4 are hydrogen, hydroxy. amino and may be identical or different; R5, R6 R7, R13 and R'b are all hydrogen: R6 and R" are both amino; Re is phenoxyalkyl or phenalkyl of one to six carbon atoms in the alkyl, or C, to C5 alkyl; R10 is C1 to C5 alkyl, C1 to C6 alkylthio or phenalkylthio of two to four carbon atoms in the alkyl; R'4 is hydrogen, hydroxy, phenyl, C1 to C3 alkylphenyl or chlorophenyl; and X, B, B1 and n have the meanings given in claim 2.
5. 5. A dye formulation as claimed in claim 1 in which A in the formula is a radical of the formula:

   in which D is hydroxy, amino, C1 to C4-alkylamino, phenylamino, phenylamino substituted by methyl. methoxy, chloro or bromo in the 4-position, alkylcarbonylamino of one to three carbon atoms in the alkyl or benzylamino:: E is bromo, acetyl, methoxycarbonyl. ethoxycarbonyl. propoxycarbonyl, butoxvcarbonyl, benzoyl, 4-methylbenzoyl, 2,4,6-trimethylbenzoyl, 4-methoxybenzoyl. i phenoxybenzoyl, N-propylaminocarbonyl, nitro, cyano, methylsulfonyl, phenylsulfonyl, 4-methylphenylsulfonyl, methoxy, or 2-oxadiazolyl or 2-thiodiazolyl which bear phenoxyalkyl or phenalkyl of one to six carbon atoms in the alkyl, C, to C5 alkyl, C, to C6 alkylthio or phenalkylthio of two to four carbon atoms in the alkyl as substituents in the 5-position; F is hydrogen, hydroxy, amino or C1 to C5 alkylamino:

   : G is hydroxy, amino, phenylamino, benzoylamino or alkylcarbonylamino of one to three carbon atoms in the alkyl; H' is hydrogen, hydroxy, amino or phenylamino and one of the substituents G and H' may be nitro; K is hydrogen, hydroxy, methyl. phenyl, 4-methylphenyl or 4-chlorophenyl; X is 4-chlorophenyl, 4-bromophenyl, 4-methoxyphenyl, 3-N,N-diethylsulfamoyl- phenyl, 4-methylphenyl, methyl, ethyl, 4-isopropylphenyl or phenyl; B is hydrogen;; B' is C1 to C5 alkyl, 2-hydroxyethyl. alkoxyalkyl of a total of three to seven carbon

   atoms, phenalkyl of a total of seven to ten carbon atoms, phenoxfalkyl of tzo to four carbon atoms in the alkyl, phenoxyalkoxyalkyl of four to six carbon atoms in the alkoxyalkyl, cyclohexyl, phenyl or phenyl in which onc hydrogen atom is substituted by fluoro, trifluoromethyl, phenalkoxy of seven to eight carbon atoms, carbonylalkoxy of a total of two to five carbon atoms, alkylaminocarbonyl or dialkylsulfamoyl of one to four carbon atoms per alkyl or phenoxy and one to three hydrogen atoms may optionally be replaced by methyl, methoxy. ethoxy, chloro or bromo and the substituents may be identical or different: or the group B-N-B1 | is a piperidine or morpholine radical and n is I or 2.
6. 6. A dye formulation as claimed in claim I in which A in the formula is a radical of the formula:

   in which D is amino; E is acetyl, benzoyl, methoxy, bromo. phenylsulfonyl or p-methyl-phenyl sulfonyl: F, G and H' each are hydroxy or amino, one or two of them being hydroxy: X is 4-chlorophenyl, 4-methoxyphenyl, 4-methylphenyl or phenyl: B is hydrogen; and B' is C3 to C, alkyl. phenalkyl of a total of eight to ten carbon atoms, alkoxyalkyl of a total of five to eight carbon atoms or phenyl in which one or two hydrogen atoms are optionally replaced by C to C4 alkyl, phenoxy, chloro and/or trifluoromethyl and the substituents may be identical or different.
7. 7. A dye formulation as claimed in any of claims 1 to 6 in which X is phenyl.
8. 8. A dye formulation as claimed in claim I in which A in the formula is a radical of the formula:

   X is phenyl; B is hydrogen; K is acetyl; and B' is isopropyl, n-butyl, 2,4-dimethylpentyl-(2), 2-ethylhexyl, p-phenylethyl or 2chloro-5-trifluoromethylphenyl; or K is methoxy; and B' is isopropyl, 2-methylbutyl-(2), n-hexyl or 2,4-dimethylpentyl-(3); or K is bromo; and B' is isopropyl; or K is phenylsulfonyl or 4-methylphenylsulfonyl; and B' is isopropyl, 2-ethylhexyl, 3-ethoxypropyl. n-pentyl, n-butyl, 4-phenylbutyl-(2), 4-benzyloxyphenyl, 4-isopropylphenyl or 4-phenoxyphenyl.
9. 9. A dye formulation as claimed in claim I in which A in the formula is a radical of the formula:

   X is phenyl; B is hydrogen: B' is 4-benzyloxyphenyl: and n is 1.
10. 10. A dye of the formula according to claim I wherein A in the formula is a radical of the formula:

    in which R' is hydrogen, bromo, chloro, nitro, cyano, C, to C4 alkylsulfonyl, phenylsulfonyl, methylphenylsulfonyl or C, to C4 alkoxy, or except when R2 is amino, R3 and R4 are hydrogen and X is phenyl or substituted phenyl, R' may alternatively be acetyl, carbonylalkoxy of one to five carbon atoms in the alkyl, benzoyl, monomethylbenzoyl, dimethylbenzoyl, trimethylbenzoyl, methoxybenzoyl, ethoxybenzoyl, phenoxybenzoyl or N-alkylaminocarbonyl of one to four carbon atoms in the alkyl;; R2 is hydrogen, hydroxy, amino, C, to C4 alkylamino, C, to C4 alkoxy, phenylamino, phenylamino substituted by C, to C5 alkyl, methoxy, ethoxy or C2 to C4 Cacyloxy with the proviso that when R', R3 and R4 are all hydrogen, R2 is other than phenylamino and substituted phenylamino;R3 and R4 are hydrogen, hydroxy, amino and may be identical or different: R6, R6, R7 and R'3 are each hydrogen; R5 and R11 are each amino; R9 is phenoxyalkyl or phenalkyl of one to six carbon atoms in the alkyl or C1 to C5 alkyl; R'O is C, to C5 alkyl, C1 to C8 alkylthio or phenalkylthio of two to four carbon atoms in the alkyl; R14 is hydrogen, hydroxy, phenyl, C, to C3 alkylphenyl or chlorophenyl; R15 is hydrogen, C1 to C5 alkyl or phenyl;; X is methyl, ethyl, 4-chlorophenyl, 4-bromophenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-alkylphenyl of one to four carbon atoms in the alkyl, 3-N,N-bis-alkylsulfamoylphenyl of one to four carbon atoms in the alkyl or phenyl; B is hydrogen; and B' is C, to C6 alkyl, 2-hydroxyethyl, alkoxyalkyl of a total of three to seven carbon atoms, phenalky.l of a total of seven to ten carbon atoms, phenoxyalkyl of two to four carbon atoms in the alkyl, phenoxyalkoxyalkyl of four to six carbon atoms in the alkoxyalkyl, cyclohexyl or phenyl in which one hydrogen atom may optionally be replaced by fluoro, trifluoromethyl, phenalkoxy of seven or eight carbon atoms, carbonylalkoxy of a total of two to five carbon atoms, alkylaminocarbonyl or dialkylsulfamoyl of one to four carbon atoms in each alkyl or phenoxy and one to three hydrogen atoms may optionally be replaced by methyl, methoxy, ethoxy, chloro or bromo and the substituents may be identical or different and n is 1 or 2.
11. 11. A dye as claimed in claim 10 and having the formula:

    in which A4 is a radical of the formula:

    in which D is hydroxy, amino, C, to C4 alkylamino, phenylamino, phenylamino bearing methyl, methoxy, chloro or bromo as a substituent in the 4-position, alkyl carbonylamino of one to three carbon atoms in the alkyl, or benzoylamino:: E is bromo, acetyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxy carbonyl, benzoyl, 4-methylbenzoyl, 2,4,6-trimethylbenzoyl, 4-methoxybenzoyl, 4 phenoxybenzoyl, N-propylaminoearbonyl, nitro, cyano, methylsulfonyl, phenylsulfonyl, 4methytphenylsuWonyl, methoxy, or 2-oxadiazolyl~or Z-thladiazolyt which bear in the 5-position phenoxyalkyl or phenalkyl of one to six carbon atoms in the alkyl, C1 to C5 alkyl, C, to C6 alkylthio or phenalkylthio of two to four carbon atoms in the alkyl as substituents; F is hydrogen, hydroxy, amino or C, to C5 alkylamino; G is hydroxy, amino, phenylamino, benzoylamino or alkylcarbonylamino of one to three carbon atoms in the alkyl;; H' is hydrogen, hydroxy or phenylamino, and one of the substituents G and H' may also be nitro; K is hydrogen, hydroxy, methyl, phenyl, 4-methylphenyl or 4-chlorophenyl; and X, B, B1 and n have the meanings given in claim 10.
12. 12. A dye of the formula according to claim 11 in which A4 is a radical of the formula:

    in which D is amino; E is methoxy, bromo, phenylsulfonyl or p-methyl-phenyl sulfonyl: F, G and H' are hydroxy or amino, one or two being hydroxy; X is 4-chlorophenyl, 4-methoxyphenyl, 4-methylphenyl or phenyl: B is hydrogen; and BS is C3 to C6 alkyl, phenalkyl of a total of eight to ten carbon atoms, alkoxyalkyl of a total of five to eight carbon atoms, phenyl or phenyl in which one or two hydrogen atoms are replaced by C, to C4 alkyl, phenoxy, chloro or trifluoromethyl and the substituents may be identical or different.
13. 13. A dye as claimed in claim 10 to 12 in which X is phenyl.
14. 14. A dye according to claim 10 of the general formula:

    in which A2 is a radical of the formula:

    in which D is amino; E is acetyl, i)enzoyl, methoxy, bromo, phenylsulfonyl or p-methyl-phenyl sulfonyl; F, G and H' are hydroxy or amino, one or two being hydroxy; Z is 4-chlorophenyl, 4-methoxyphenyl, 4-methylphenyl or phenyl; and B4 is C3 to C6 alkyl, phenalkyl of eight to ten carbon atoms, alkoxyalkyl of a total of five to eight carbon atoms or phenyl which optionally bears C, to C4 alkyl, phenoxy, chloro and/or one trifluoromethyl as a substituent, the number of substituents being one or two.
15. 15. A dye as claimed in claim 10 of the general formula:

    in which K is methoxy; and M is isopropyl, 2-methylbutyl-(2), n-hexyl or 2,4-dimethylpentyl-(3): or K is bromo; and M is isopropyl; or K is phenylsulfonyl or 4-methylphenylsulfonyl; and M is isopropyl, 2-ethylhexyl, 3-ethoxypropyl, n-pentyl, n-butyl, 4-phenylbutyl-(2), 4-benzyloxyphenyl, 4-isopropylphenyl or 4-phenoxyphenyl.
16. 16. The dye as claimed in claim 10 which has the formula:
17. 17. A dye formulation as claimed in claim 1 wherein the dye is as claimed in any one of claims 10 to 16.
18. 18. A dye or dye formulation as claimed in any of claims 1 to 17 and specified in any of the foregoing Examples.
19. 19. A method of dyeing or printing cellulose or cellulosic fibrous material wherein the cellulose or cellulosic fibrous material is treated with a dye formulation as claimed in any one of claims I to 9, 17 or 18.
20. 20. A method of dyeing or printing cellulose or cellulosic fibrous material as claimed in claim 19 carried out substantially as described in any one of Examples I, 66, 111, 176, 198, 294, 315, 326, 349 or 366.
21. 21. Textile material of cellulose or cellulosic fibrous material which has been dyed and/or printed with a dye formulation as claimed in any of claims 1 to 9, 17 or 18.