CS198134B2 - Method of preparing with fibre reactive dyes - Google Patents

Description

CZECHOSLOVAK SOCIALISTIC

(19)

DESCRIPTION OF THE INVENTION

KPATENTU 198134 (11) (Bl)

INVENTORY OFFICE DISCOVERY (22) Enrolled 27 12 73 (21) (PV 9036-73) (32) (31) (33) Priority from 29 12 72 (19076/72) Switzerland (51) Int. Cl.3 C 09 B 50/10 (40) Published 31 08 79 (45) Published 15 02 83 (72)

The inventor of HEGAR GERT dr., SCHONENRUCH (Switzerland) (73)

Patent proprietor of CIBA-GEIGY AG, BASILE (Switzerland) (54) Method for preparing fiber reactive dyes 1

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for the preparation of color-reactive fibers of the formula I

where one Y is a sulfo group and the other Y is a group of the formula

-NH - c c -Z

I II

IN

C 1 Br 4) wherein Z is chlorine or bromine, C 1 -C 4 alkoxy, substituted carboxy, C 1 -C 4 alkoxyalkoxy, phenoxy substituted by chlorine, nitro, carboxy and sulfo; -ce-NH 2, (C 1 -C 4 -alkyl) alkylamino, optionally substituted by chlorine, hydroxy, carboxy or sulfo, N, N-dialkyl-C 1 -C 4 -alkyl, substituted optionally an hydroxy group, furthermore a C 1 -C 4 alkoxyalkyl amino group, an N-methyl-N- (3-sulfoethylamino) group; ureido, N-alkyl-N-phenylaminosctipines having 1 to 4 carbon atoms in the alkyl, benzylamino, cyclohexylamino, morpholino, piperidino, piperazino, phenylamino, optionally substituted with chloro, nitro, methyl, the methoxy, ethoxy, acetylamino, hydroxy, carboxy, sulfo and sulfomethyl groups further include N-sulfomethyl-N-phenylamino or naphthylamino which is optionally substituted with sulfo and hyd- 198134 198134 4 xyloxy and halo is a chlorine, bromine or fluorine atom which is characterized by condensing a dye of the formula I wherein one Y is a sulfo group and the other Y is an acylating amino group, with 2,4,6-trichloro-triazine or 2,4,6- tri-bromo-sym-triazine, which is optionally condensed with a compound represented by

H-Z wherein Z is other than chlorine, optionally bromine.

The acylating agents are 2,4,6-trichloro-1,3,5-triazine, optionally 2,4,6-tribromo-1,3,5-triazine and in particular 4,6-dichloro-1, 3,5 -triazines, which are substituted at the 2-position by an aliphatic or aromatic radical via an atomsily bonded mercapto group, or an oxygen-linked or, in particular, amino group, or an aliphatic, heteroaliphatic or aromatic amine compound bonded via a nitrogen atom. Examples of such compounds which may be bound to the 2-position of the triazine core by reaction with trihalentriazines are the following: aliphatic or aromatic mercapto compounds or hydroxyl compounds such as thioalcohols, thioglycolic acids, urea, thiophenols, methyl alcohol, ethyl alcohol, isopropyl alcohol, glycolic acid, phenol, chlorophenols, or nitrophenols, phenoxycarboxylic and phenol sulfonic acids, naphthols, naphthol sulfonic acids, etc., especially ammonia and acylating amino groups containing compounds such as hydro -xylamine, hydrazine, phenylhydrazine, phenylhydrazinesulfonic acids, carbamide acids and their derivatives, semi- and thiosemicarbazides and semi- and thiocarbazones, methylamine, ethylamine, isopropylamine, methoxyethylamine, methoxypropylamine, dimethylamine, diethylamine, methylphenylamine, ethylphenylamine, chlorethylamine, ethanolamines, propanolamiums, benzylamine, cyclohexylamine, morpholine, pip eridine, piperazine, ammonium carbonate ester, aminoacetic acid ethyl ester, aminoethanesulfonic acid, N-methylaminomethanesulfonic acid, especially butaromatic amines such as aniline, N-methylaniline, toluidines, xylidines, chloroanilines, p- or m -aminoacetanilide, nitranilines, aminophenols, nitrotoluidines, phenylenediamines, toluylenediamines, anisidine, phenetidine, diphenylamine, naphthylamine, aminonaphthols, diaminonaphthalenes, and especially acidic groups containing anilines such as sulfanilic acid, methanilic acid, orthanilic acid, anilindisulphonic acid, aminobenzyl sulphonic acid, aniline, ω-methanesulphonic acid, -naphthylaminodisulphonic acid and tri-sulphonic acid, aminobenzoic acids such as 1- or 2-oxy-5-aminobenzoic acid, aminonaphthol mono-, - di- and trisulfonic acid, aminobenzoic sulfonic acid, etc.

The introduction of such groups into the triazine core is possible as needed prior to reaction or after reaction of halidriazine with the formazan dye containing the amino group. It is also possible to initially react the amine group containing the dye with the 2,4,6-trihalogen! with 1,3,5-triazine, especially with cyanuric chloride, and then, in the case of the dihalo-triazine residue obtained, replace the halogen by reaction with one or, if appropriate, different compounds. Furthermore, it is also possible in the barium prepared by the above process which has β-chloropropionyl and (S-dichloropropionyl or ω, β-dibromopropionyl group, to convert this group sufficiently in accordance with the invention by removal of the hydrogen halide with alkali reactants to non-saturated). an acyl radical, for example an acrylic radical, a chloroacrylic radical or a bromo-acrylic radical.

The dyes prepared by the process of the invention are preferably isolated by low salinity and filtration, depending on the low temperature. Optionally, the filtered dyes can be dried after the addition of preservatives and / or ointments, for example after the addition of a mixture of equal parts of mono-sodium phosphate and disodium phosphate; preferably, the drying is carried out at low temperatures and under reduced pressure. By spray-drying the whole of the semifinished product mixture, in certain cases, it is possible to prepare dry preparations according to the invention, that is to say, it does not have to temporarily isolate the colorant.

The dyes prepared by the process of the invention are suitable for dyeing and printing various materials, such as silk, leather, wool, polyamide fibers and urethane fibers, especially materials containing cellulose fibers such as linen, pulp, regenerated cellulose and mainly wool. In particular, it is suitable for dyeing on a blender, in which the goods are impregnated with aqueous or, if appropriate, salt-containing dye solutions, and the dye is fixed or heat-treated after alkaline treatment or in the presence of alkali.

The dyes prepared according to the invention are also suitable for printing, in particular for printing on cotton, but also for printing on nitrogen-containing fibers, such as wool, silk or woven fabrics containing wool.

It is advisable to rinse the dyes or prints thoroughly with cold and hot water, optionally with the addition of dispersing and promoting diffusion-fixed dye components.

The dyes produced by the process according to the invention are distinguished by their excellent dissolvability, which are not chemically bound to the fiber. In this respect, the dyes already known in the art, such as those described in Swiss Patent Publication No. 394,440, are in excess of them.

The new dyes already provide a shade with high wet fastness at a shorter time of 198134 and less scrubbing work. It is also not necessary to use water-free electrolytes for washing. In the following examples, parts are by weight and temperatures are given in ° C. Example 1 67.6 parts of copper complex compound N - (2-hydroxy-3-amino-5-sulfo-phenyl) -N- (2 '- carboxy-4'-sulfophenyl) -ms- (2-chloro) -5-sulfophenylformazan (prepared coupling of 6-acetylamino-2-amino-1-hydroxybenzene-4-sulfonic acid with 2-chloro-5-sulfobenzaldehyde hydrazone and 2-carboxy-4-sulfophenylhydrazine by conventional procedures) and then saponification with the compound of Example 1 and saponification of the acetylamino group with dilute sodium hydroxide) are dissolved in 1200 parts of water with neutral reaction and the solution is mixed with 20.8 parts of 2-isopropoxy-4,6-dichloro-triazine. 30 ° C is maintained at a pH of 6 to 6.5 by addition of sodium hydroxide.

Once the original dye is no longer detectable, the product is salted out by the addition of sodium chloride and filtered off. Wash the dye with dilute sodium chloride solution and dry under vacuum. The color of the cotton is the permanent blue shades.

If complex copper compounds and reactive acylation agents are used in the following table, valuable blue dyes will also be obtained.

Copper Complex Compound Acylation Compound Shade 2 N- (2-Hydroxy-3-amino-5-sulfo-phenyl) -N'- (2'-carboxy-4'-sulfenyl-phenyl-2 '- chloro-5-sulfophenyl-2-ethoxy-4,6-dichloro-1,3,5-triazine blue 3 N- (2-hydroxy-3-amino-5-sulfophenyl) -N 2-Amino-4,6-dichloro-1,3,5-triazine - (2'-carboxy-4'-sulfo-phenyl) -ms- (2-chloro-5-sulfo-phenyl) -formazan blue 4 N- (2-Hydroxy-3-amino-5-sulfo-phenyl] -N'- (2'-carboxy-4'-sulfo-phenyl) -ms- (2-chloro-5-sulfo-phenyl) N- (2-hydroxy-3-amino-5-sulfo-phenyl) -N- (2'-sulfophenylamino) -4,6-dichloro-1,3,5-triazine blue 2- (2'-Carboxy-4'-sulfonyl-phenyl) -s- (2-chloro-5-sulfo-phenyl) -formazan 2- (2 ', 5'-disulfo-phenylamino-4,6-di) chloro-1,3,5-triazine-blue 6 N- (2-hydroxy-3-amino-5-sulfophenyl) -N'- (2'-carboxy-4'-sulfonyl) -ms- ( 2-chloro-5-sulfo-phenyl) -formazan 2,4,6-trichloro-1,3,5-triazine-blue 7 N- (2-hydroxy-3-amino-5-sulfo-phenyl) -N ' - (2'-carboxy-4'-sulf of phenyl) -ms- (2-chloro-5-sulfophenyl) formazan 2-methoxy-4,6-dichloro-1,3,5-triazine blue 8 N- (2-hydroxy-3-amino-5- -sulfo-phenyl) -N'- (2'-carboxy-4'-sulfo-phenyl) -ms- (2-chloro-5-sulfo-phenyl-2-chloro-5-sulfo-phenyl) -isopropoxy N- (2-hydroxy-5-amino-3-sulfophenyl-N '-( 2 ' -carboxy-4 ' -sulfonyl) -3,6-dichloro-1,3,5-triazine blue -ms- (2-chloro-5-sulfo-phenyl) -formazan 2- (2'-ethoxyethoxy) -4,6-dichloro-1,3,5-triazine blue 198134

Copper Complex Compound Acylation Compound Shade N- {2 "hydroxy-5-amino-3-8-phosphophenyl-N'- (2'-carbonyloxy-4'-sulfophenyl) -m- (2-chloro-5- sulfophenyl 2-isopropoxy-4,6-dichloro-1,3,5-triazine blue N- (2-hydroxy-5-amino-3-sulfophenyl-N '-( 2 ' -carb-OXy) -4'-sulfonyl) -s-12-chloro-S-sulfonyl) -formazan 2- (4'-sulfonylamino) -4-, 6-dichloro-1,3,5-triazine blue N- (2-hydroxy-5-amino-3-sulfophenyl-N '-( 2 ' -carbxy-4 ' -sulfophenyl) m- (2-chloro-5-sulfophenyl) formazan 2 , 4,6-trichloro-1,3,5-triazine blue N * (2-hydroxy-3-amino-5-sulfophenylamino) -N '- (2'-carboxy-5'-sulfo- phenyl) -ms- (2-chloro-5-sulfophenyl) formazan 2-isopropoxy-4,6-dichloro-1,3,5-triazine blue M- (2-hydroxy-3-amino-5-- sulphophenylamino) -N '- (2'-carboxy-5'-sulfo-phenyl) -ms- (2-chloro-5-sulfonyl) formazan 2-amino-4,6-dichloro-1, 3,5-triazine blue N- {2-hydroxy-3-amino-5'-sulfenylamino} - (2'-carboxy-5'-sulfo-phenyl) - (2 -chloro-5-sulfonyl-1-formazan 2-ureido-4,6-di-tert-1,3,5-triazine blue N- (2-hydroxy-3-amino-5-sulfo) enylamino} -N '- (2'-carboxy-5'-sulfo-phenyl) -ms- (2-chloro-5-sulfonyl) formazan 2-ethoxy-4,6-dichloro-1 3,5-triazine blue N- (2-hydroxy-3-amino-5-sulfenylamino) -N '- (2'-carboxy-5': sulfo-phenyl) -ms- (2- chloro-5-sulfonyl) formazan 2- (4'-sulfophenoxy) -4,6-dihydro-1,3,5-triazine blue N- (2-hydroxy-5-amino-3-sulfone) 2-isopropoxy-4,6-dichloro-enyl) -N'- (2'-carboxy-5'-sulfonyl) -ms- (2-chloro-5-sulfonyl) -formazan N- (2-Hydroxy-5-amino-3-sulfenyl) -N '-( 2 ' -carboxy-5 ' -sulfonyl) - (1,3 ' -triazine blue) ( 2-chloro-5-sulfonyl) -formazan 2- (2 ', 5'-disulfophenylamino) -4,6-dichloro-1,3,5-triazine blue N- (2-hydroxy-5 -amino-3-sulfonyl) -N'- (2'-carboxy-5'-sulfophenyl) -ms- (2-chloro-5-sulfophenyl) -2-methylamino-4,6- di-chloro-1,3,5-triazine blue formazan

Claims (3)

19 813 4 Number Copper Compound 21 N- (2-Hydroxy-5-amino-3-sulfophenyl) -N'- (2'-carboxy-5'-sulfenylphenyl) -2- (2-chloro 5-sulfophenyl) -formazan 22 N- (2-hydroxy-3-amino-5-sulfiophenyl) -N- (2'-carboxy-4'-sulfonyl) -ms- (2-fluoro) N- (2-hydroxy-3-amino-5-sulfophenyl) -N'- (2'-carboxy-5'-sulfophenyl) -5-sulfo-phenyl) -formamide; -Bromo-5-sulfo-phenyl) -formazan 8 Acylating agent Shade 2-morpholino-4,6-dichloro-1,3,5-triazine blue 2-isopropoxy-4,6-dichloro-1,3, 5-triazine blue 2-isopropoxy-4,6-dichloro-1,3,5-triazine blue Dissolve 2 parts of the dye with 0.5 part of m-nitrobenzenesulfonic acid sodium salt to impregnate with cotton. Then the fabric is impregnated with a solution of 20 ° C, which contains 5 g of sodium hydroxide and 300 g of sodium chloride per liter, and is then colored to a 75% weight, dyed steaming after at 60 DEG C. to 60 DEG C., rinsed, washed for three hours in 0.3% boiling solution of a non-ionic detergent, rinsed and dried. The printing of 2 parts of the dye is quickly poured into 100 parts of a stub dirt containing 45 parts of 5% sodium alginate, 32 parts of water, 20 parts of urea, 1 part of m-nitrobenzenesulfonic acid, and 2 parts of carbonate. sodium salt. The paste prepared in this way prints the woolen fabric on a cylindrical printing machine and the printed fabric obtained is steamed for 6 to 8 minutes at 100 ° C. The printed fabric is then rinsed thoroughly with cold and hot water, with the chemically unfixed fibers removed with the fibers and finally dried. SUBJECT MATTER A process for the preparation of dye reactive dyes of the general formula I, wherein one Y is a sulfo group and the other Y is a group of the general formula NH-C-Z-HWN in C 1-6 -n, where Z is chlorine or bromine, C 1 -C 4 alkoxy, optionally substituted by carboxy, alkoxy-alkoxy-C 1 -C 4 -alkyl, phenoxy-group-substituted by chlorine, nitro , carboxy and sulphosine, an amino group of the formula -NH 2, an alkyl-amino group having from 1 to 4 carbon atoms substituted by a chlorine atom, a hydroxy group, a carboxy group or a sulphonate, až, a Ν-dialkylamino group having from 1 to 4 carbon atoms substituted by an optionally hydroxy group , C 1 -C 4 alkoxyalkylamino, N-methyl-N- (1-sulfoethylamino, ureido, N-alkyl-N-phenylamino) C 1 -C 4 -alkyl, benzylamino, cyclohexylamino, morpholino, piperidino, piperazino, phenyl-amino optionally substituted with chlorine, nitro, methyl, methoxy, ethoxy, .alpha.-cetyl amino , hydroxy, carboxy, sulfo and sulfomethyl, N-sulfomethyl-N-phenylamino or naphthylamino substituted by sulfo and hydroxy, halo, chloro, bromo or fluoro, for dyeing and printing characterized in that the dye of formula (I) is present, wherein each Y is a sulfo group and the other is Y is an acylated amino group, with 2,4,6-trichloro-triazine not or with a 2,4,6-tribromo-triazine which optionally condenses or condenses with the dye to form a compound of the general formula H-Z wherein Z is other than chlorine or bromine. 2. A process as claimed in claim 1, wherein the compound of formula (I) is one wherein Y is sulpho and the other is acylated and h is chloro. 3. A process as claimed in claim 2, wherein the 2,4,6-trichloro-triazine is condensed with i-propanol and the 2-isopropoxy-4,6-di-chloro-triazine obtained is condensed with a complex copper compound. N- (2-Hydroxy-3-amino-5-sulfonyl) -N '- (2'-carboxy-4'-sulfonyl) -ms- (2-chloro-5-sulfophenyl) f ormazanu. severografia, n. p., plant 7, Most