DE2020295A1 - Dye preparation and process for their production - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

, Case 67 60 ^ 1

Germany " .-

Dye preparations and processes for their manufacture.

Various dye preparations have already been proposed, 'which mainly consist of a solution Dye exist in an organic solvent. These preparations have the advantage that, in contrast to the usual dye powders, they do not dust and the dyes it contains are not ground so finely and must be conditioned, as is the case with dye powders the case is. But since the admixture of solvents is compulsory. The water pollution increases and the solvents used with the dyes are practically not recovered there was a need for '

0098 47/177 7

Dye preparations that contain the highest possible proportion of dye.

It has now been found that dye preparations with phosphorus-containing solvents, in particular with hexamethylphosphoric acid triamide, meet the above-mentioned requirement and, moreover, are still practically non-flammable, which is the handling of the preparations facilitated.

The present invention therefore relates to dye preparations the a) a dye, b) a solvent which is a phosphorus derivative, preferably hexamethylphosphoric triamide, optionally c) a dispersant and optionally d) a further solvent contain.

As a rule, the dye preparation will contain at least $ 20, preferably $ 25 to $ 50 (based on the weight of the dye preparation) of dye, with up to $ 0% of the phosphorus thiamide present, if a liquid dispersant with good dissolving power is used

the disperser can be replaced.

Representatives of the most varied classes come into consideration as dyes, namely a) substantives containing sulfo groups Dyes, acidic wool dyes and especially acidic fiber-reactive dyes and b) preferably

009847/1777

Metal complex dyes free of sulfo groups, quaternized Dyes suitable for spin dyeing cellulose acetate and lacklb'sliohe dyes and especially disperse dyes, which also have fiber-reactive groups or can be free thereof.

The dye definitions given above correspond usually the terms used in the Color Index.

The dyes can belong to a wide variety of dye classes, such as the classes of mono-, dis- and polyazo dyes, anthraquinone, perinone, quinophthalone, Oxazine, nitro, phthalocyanine, stilbene and methine dyes, including the styryl, azamethine, polytnethin and azostyryl dyes.

From the particularly preferred series of disperse dyes, there are above all the mono- and azo dyes Disazo series in question. Examples are the dyes Formula,.

DN = NA-NR ₁ R ₂ ,

wherein D is the radical of a diazo component, A is the radical of an optionally substituted p-arylene radical and R, and Rp are in each case optionally substituted alkyl radicals which can be the same or different from one another and the dyes of the formula

00 9 8 47/1 7 77 bad original

D-N = N-B,

where D is the same as above and B is the remainder of an enolizable coupling component such as a naphthol, phenol, Pyrazolones or aminopyrazoles is called. Furthermore, the disazo dyes come into question, especially those that differs from p-phenylazo-azobenzene of the formula

derive.

Examples of suitable anthraquinone dyes are e.g. the optionally substituted 1,4-diamino, l-Bydroxy-4-amino- and!, S-dihydroxy- ^ ß-diaminoanthraquinones called.

The azo dyes can be derived from the following diazo components D-NH ₂ :
Aminobenzene,
1-amino-4-chlorobenzene,
l-amino-4-bromobenzene,
1-Amino-Jj-methylbenzene,
l-amino- ^ l-nitrobenzene,
1-amino - ^ - cyanobenzene,
l-amino-2,5-dicyanobenzene,
l-amino- ^ l-methylsulfonylberizole,

009847/1777

l ~ Amino-4-carbalkoxybenzene, l-Amino-2,4-dlchlorobenzene, l-Amino-2 _> 4-dibromobenzene, l-Amino-2-methyl- ⁱ f-chlorobenzene _A l-Amino- ^ - trifluoromethyl- ^ -chlorobenzene, 1-amino-2-cyano-4-chlorobenzene, l-amino-2-carbomethoxy-4-chlorobenzene, * l-amino - ^ - carbomethoxy - ^ - nitrobenzene, l-amino-2-chloro- 4-cyanobenzene _J l-amino ^ -chlor - ^ - nitrqbenzene, l-amino-2-bromo-4-nltrobenzene, l-amino-2-chloro-4-carbethoxybenzene, l-amino-2-chloro-4-methylsulfonylbenzene _ί l-Amino-2-methylsulfonyl-4-chlorobenzene, l-Amino-2,4-dinitro-6-mefchylsulfonylbenzene,

l-anlino-2,4-dlnltro-6- (2'-hydroxyethylsulfonyl) benzene,

l-amino-2,4-dinitro-6 "- (2'-chloroethylsulfonyl) benzene, l-Amino ^ -methylsulfonyl ^ -nitrobenzene,

l-Amino - ^ - methylsulfonyl ^ -nitrobenzene, ·

l-amino-2,4-dinitrobenzene, l-amino-2,4-dleyanbenzene, l-amino-2-cyano-4-methylsulfonylberizol ₁ l-amino-2,6-dlchlor-4-cyanobenzene,

009847/1777

l-amino-2,6-dlchlor-4-nitrobenzoX, l-Amino ^^ - dicyan-o-chlorobenzene, ty-amino-benzoic acid cyclohexyl ester, l-Amlno-2, ^ - dinlbro-6-chlorobenzene and especially l-Amino ^ -cyan - ^ - nitrobenzene, also

l-aminobenzene-2-, -3- or - ^ - sulfonic acid amides, such as the N-methyl or Ν, Ν-dimethyl or diethyl amide, ^v N, 7-isopropyloxypropyl-2-aminonaphthalene-6-sulfonic acid amide N _ί 7-Isopropyloxypropyl-l-aminobenzene-2-, -5- or - ^ - sulfonic acid amide,

N-Isopropyl-1-aminobenzene-2-, -5- or - ^ - sulfonic acid amides N, 7-methoxypropyl-l-aminobenzene-2-, -5- or -4-sulfonic acid amide, N, N-bis (ß-hydroxyethyl) -l-aminobenzene-2- ', -5- or -4-sulfonic acid amide,

1-Amino-4-chlorobenzene-2-sulfonic acid amides and the derivatives N-subsfcituierten '2,5- or 4-Aminophenylsulfamat, ^2-amino-1 I--, -5- or -6-methylphenylsulfamate, 2-amino-5 -methoxy-phenylsulphamate, ^ -amino-o-chlorophenylsulphamate, 3-amino-2,6-dichlorophenylsulphamate, 4-amino-2- or -3-methoxyphenylsulphainate, N, M-dimethyl-2-aminophenylsulphamate,

009847/1777 "

N / N-DI-n-butyl-2-aminophenylsulphamate, N, N-dimethyl-2-amino- ⁱ J-chlorophenylsulphamate, !!, n-propyl - ^ - aminophenylsulphamate, K ^ N-di-n-butyl- I-aminophenylsulphanate, 0 - () - aminophenyl) -N-morpholine-N-sulphonate, 0- (2-aminophenyl) -N-plperidin-sulphonate, N-cyclohexyl-O-i-aminophenyl-sulphamate, K- (N -Methylaniline) -0-5- (aminophenyl) -sulphonate, NjlJ-diethyl - ^ - amino-G-methylphenyl-sulphamate, N-ethyleneimine-0- (4-aminophenyl) -sulphonate, l ^ N-dimethyl - ^ - atninophenylsulphainate, G- (n-propyl) -0- (5-aminophenyl) -sulphonate, Oiss-chloroethyl-O-CS-aminophenylJ-sulphonate, 0-benzyl-0- (3-aminophenyl) -sulphonate and O-ethyl- Oi ^ -rAmino-Siö-dimethyl-phenyl-sulfonate,

5 _J 2 ^l -Diinethyl- ⁱ l-aminoazobenzene, 2-methyl-5-methoxy- ^ί f-aminoazobenzene, il-amino-S-nitroazobenzene,

^l \ '-Methoxy - ^ - aminoazobenzene, 2-Me ^ yI -' * '- methoxy-M-aminoazobenzene, 3 / 6,4'-trimethoxy - ^ - aminoazobenzene,

0098U / 1777

4'-chloro-4-aininoazobenzene, 2'- or 3'-chloro-4-aminoazobenzene, 3-nitro-4-amino-2 ', 4'-dichlorazobenzene and 4-aminoazobenzene-4'-sulfonic acid amide, 2-aminothiazole, 2-amino-5-nitrothiazole 2-amino-5-methylsulfonyl-thiazole, 2-amino-5-cyanthiazole, 2-amino-4-methyl-5-nitrothiazole, 2-amino-4-methylthiazole, 2-amino-4-phenylthiazole, 2-Amino-4- (4'-chloro) -phenylthiazole, 2-Amino-4- (4'-nitro) -phenylthiazole, 3-aminopyridine, 3-aminoquinoline, 3-aminopyrazole, 3-amino-l-phenylpyrazole, 3-aminoindazole, 3-amino-l, 2,4-triazole,.

5- (methyl-, ethyl-, phenyl- or Bonzyl) -1,2,4-triazole,

3-amino-1- (4'-methoxypheny1) -pyrazole, 2-aminobenzothiazole, 2-amino-6-methylbenzthiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-chlorobenzothiazole,

2-amino-6-cyallbenzthiazole, 3-Ar, 1 no-5 j 7 ~ di brom-ben zi s ο thiazol, 3-aniino-beriziiiothiazole, 3-Amino-'3-riitro-7-bromo-benzisothiazole, 0 0 98 A 7/1777

BATH ORIGINAL

'■■■ .'- - 9 -

3-AmIno-5'-nitro-benzisot'niazole, 3 _i i? -Diamino-5-nitro-benzisothiazole, 3-amino-5-chlorobenzisothiazole, 3-amino-5-chloro-7-broITl-benzisothiazole,

* 2-Amlno-6-thiocyanthiazole, 2-amino-6-nitrobenzthiazole, 2-amino-6-carboethoxybenzothiazole,

2-Amino- (4- or 6) -methylsulfonylbenzthiazole, '·

2-Amino-1,3,4-thiadiazole, 2-amino-1,35 "fchiadiazole _i - 2-Amino-4-phenyl- or - ^ - methyl-10jS-thiadiazole, 2-amino-5-phenyl-1 , 3> 4-thiediazole, 2-amino-3-nitro-5-methylsulfo-thiophene, 2-amino-3,5-bis- (methylsulfo) -thiophene, 5-amino-3-methyl-isothiazole, 3 ~ or 4-aminophthalmide.

The water-soluble azo dyes can be fiber-reactive Contain groups such as s-triazinyl radicals on the triazine ring Carry 1 or 2 chlorine or bromine atoms, pyrimidyl radicals,

■ the one or two chlorine atoms or one or two arylsulfonyl or carry alkanesulfonyl groups on the pyrimidine ring, mono- or Bis (7-halo-ß-hydroxypropyl) -amino groups, β-haloethylsulfamyl radicals, β-haloethoxy groups, β-haloethyl mercapto groups, 2-chloro-benzthiazolyl-6-azo groups, 2-chloro-benzthiazolyl-6-azo groups, 2-chlorobenzth ± azolyl-6-amino groups, ■ 7-halogen-ß-hydroxy-pr.opylsulfamylreste, chloro-acetylamino groups, α, β-dibromopropionyl groups, vinylsulfonyl groups and

'2,3-epoxypropyl groups. ■

000847/1777

■ - ίο -

Suitable fiber-reactive diazo components are e.g. N, β-chloroethyl ^ -chlor - ^ - amino-benzenesulfamide (hydrochloride), Njß-chloroethyl - ^ - aminobenzol-sulfamid (HydrochlorLd), 3 "bromo-4-amino-u) -chloracetophenon,

N, 7-chloro-β-hydroxypropy1-4-aminobenzene-sulfamide, N, β-chloroethyl-1-amino-4-naphthylsulfonamide, N, β-chloroethyl-1-amino ^ iS-diehlorbenzenesulfamide and 4 - (7 -Chlor-β-hydroxy-propoxy) -ani1ine.

As coupling components H-B, there may be mentioned, for example; N, β-cyanoethyl-N-methyl-aniline, N, N-bis (ß-cyanoethyl) -aniline, N-ethyl-N-Cdimethylaminoethyl) -aniline, N, N-Di-β-hydroxyethyl-aniline, N-ethyl-N- (β-trimethylammoniumethyl) aniline, N-ethyl-N- (β-pyrimidiniumethyl) aniline, .1-N-β-cyanoethyl-N-ethyl-amino ~ 3-methylbenzene, N-ethyl-N- (β, ΐη-pyridylethyl) aniline, 1-N-β-cyanoethyl-amino-3 ~ roethylbenzene, 1-M, N-Di-ß-hydroxyethyl-amino-3-rhodanobenzene, N-ß-cyanoethyl-naphthsultam- (1,8), 1-N, N-Di-ß-cyanoethyl-3-methyl-aminobenzene, N, β-cyanoethyl-N, β-hydroxyethyl-aminobenzene, N, β-cyanoethyl-2-methyl-indole, Ν, β-cyanoethyl-tetrahydroGhinolin, N-Pheny1-aminobenzene,

801847/1777

^J i -Hyd roxy-1-methy1 quinone 1 in - (2), 1-hydroxy-3-methyl-benzene, 8-hydroxyquinoline, ^{3-cyano-2,6-dihydroxy-i} i-methylpyridine, 1,3! Dioxybenzene, 2-naphthylamine-5-sulfotπethylamide, 1-oxy-3-cyanmethylbenzene, 1-phenyl-3-methy! -5-pyrazolori, acetoacetate, and anilines of the formula

wherein c and d are hydrogen atoms, lower alkyl, alkoxy or Are alkyl mercapto radicals or optionally substituted phenyl, phenoxy or benzyl radicals.

In addition to the groups mentioned above, group c can also be a chlorine or bromine atom, a trirluoromethyl group and an optionally alkylated, preferably ir.ethylated acylamino group on the nitrogen atom, in which the acyl radical is the radical of an organic monocarboxylic acid, a organic conosulphonic acid, such as methane, ethane or p-toluene monosulphonic acid, or the remainder of a carbamic acid or

a KollenpUuremonoester or Mönoamide, such as phenoxycarbonyl, Is kethoxycarbonyl and aminocarbonyl.

0098A7 / 1777

BATH ORIGINAL

The groups R _{1 and R p} can be hydrogen atoms or lower alkyl groups, ie containing up to 1 to 4, preferably 2 to k carbon atoms, such as methyl, ethyl, n-propyl or n-butyl groups, which can be substituted in the usual way such as benzyl, ß-phenethyl, halogenated alkyl groups, such as β-chloroethyl, β, β, ß-trifluoroethyl, ß, 7 ~ dichloropropyl or 3 ~ chloro-2-hydroxypropyl, ß-cyanoethyl, Alkoxyalkyl, such as β-ethoxyethyl or S-methoxybutyl, hydroxyalkyl, such as β-hydroxyethyl, β, 7-dihydroxypropyl, nitroalkyl, such as β-nitroethyl-j acylaminoalkyl, such as β- (acetyl or pormyl ) -aminoäthyl-, Pettsäureacyloxyalkyl-, such as formyloxyalkyl-, ß-acetyloxyäthyl-, ß, 7-dia'cetoxypropyl- and 7-butyryloxypropyl-, ß- (alkyl or aryl) -sulfonylalkyl-, such as β-methanesulfonylethyl, ß Ethanesulfonylethyl, vinylsulfonylalkyl, phenylsulfonylalkyl and ß- (p-chlorobenzenesulfonyl) ethyl, alkyl or arylcarbamoyloxyalkyl, such as β-methylcarbamyloxyethyl, butyl carbamyloxyethyl and β-phenylcar bamyloxyäthyl-, alkyl- or aryloxycarbonyloxyalkyl-, like ß- (methoxy-, ethoxy-, ß'-chloroethoxy-, isopropyloxy- or p-Töluyloxy) -carbonyloxyäthyl-, 'Y-acetamidopropyl-, ß- (p-nitrophenoxy) - ethyl-, ß- (p-hydroxyphenoxy) -ethyl-, ß- (βV-acetylethoxycarbonyl) -ethyl-, ß - [(ß '- cyano-, hydroxy-, methoxy- or acetoxy) -ethoxycarbonyl-ethyl-, Cyanoalkoxyalkyl, ß-carboxyethyl, ß-acetylethyl, ß-diethylaminoethyl, ß-cyanoacetoxyethyl, ß-benzoyloxyethyl and ß- (p-alkoxy or phenoxy-benzoyl) -oxyethyl groups.

0098-47 / 1777

The groups R ₁ and R 3 generally contain "" no more than 18 carbon atoms.

Azo dyes to be used in the present invention are e.g. the dyes of the form in:

oil

-N = N-

CN

OCOCH

GN

G ₂ H ₄ -CN

Cl

H = N-

Gl

NHCOCH.

Il

C-N = N-

Cl

^ N = N- <I> -N (C ₂ H ₄ CN), CH,

Cl

-N = N-

Cl

-N

Cl

-N = Nr ^ <> --N <C ₂ H ₄ OCOCH ₅ )

O ₀ N-

There are also dyes of the formulas

l) ~ fklT- ~ HÜ-CR ¹

Il Il and R "

Lu question in which X = K) H or -NH ₀ , R ¹ = H ₁ -CH ,, "CONH ₂ or -UOC) C ₀ IIf .., Pl" ~ "Il or" ü-H _r and A a Phenol ™ or Haphtholrest is substituted if the reiter. can be"

008847/17 V 7 · "■ BAD

Styryl dyes to be used according to the invention are those of the formula

NC

C = CH

where R ₁ and R _{2 have} the same meaning as above, C ^{1 is} a hydrogen atom or ^{4 is} a methyl group, and Y is a cyano, carbalkoxy or arylsulfonyl group, such as, for example, a carbethoxy or phenylsulfonyl group.

May be mentioned e.g. the dyes of the formulas:

NC

> C = CH NC

GH,

NC

CO

NC C ₂ H ₄ OCONHC ₆ H ₅

009847/177

HC CH "

5/2 CH,

CH ^{N /} ■ *

NC \ C.

C = CH-CZ) "" ^{11 CH} 3

NC C ₀ H ^

2 4

Suitable anthraquinone dyes are, for example, halogenation products of the l ^ -dihydroxy - ^^ S-diamino-anthraquinone, such as 2- or ^ -Bromo-l ^ -dihydroxy- ^ S-diamino-anthraquinone, JjY-dibrom-ljS-dihydroxy-tyjS- diamino-anthraquinone, also 1,4-diamino-2,5-dichloro-anthraquinone,. l, 4-diamino-5-nitro-anthraquinone,
l-Amino-2-phenoxy-4-hydroxy-anthraquinone, l-amino-2-phenylmercapto- ^ί ^ -hydroxy-anthraquinone, l-amino-2- (ß-hydroxyäthyloxy) - ^ - hydroxy-anthraquinone and l-amino -2- (β-methoxyethyloxy) -4-hydroxy-anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -5- (3 ^f -methoxy-4 ^T -hydroxyphenyl) -anthraquinones

1,5-dihydroxy-4,8-diamino-2- or -3- (4'-hydroxy- and / or 4'-methoxyphenyl) anthraquinones

l, 5-dihydroxy-4,8-diamino-2 ~ or -5- (4'-hydroxy-2 raethylphenyl ^t) -anthraquinones l, 5-dihydroxy-4-amino-8-acetoxyäthylamino-2- or -5- (4'-hydroxyphenyl) -anthraquinpn, 1,4-013011 ^ 0-2, J-anthraquinone-di-carboximide, "1-hydroxy-4» arnino ~ 2 _i 5-anthraquinone-dicarboximide _J

009847/1777

-i> '-phenylemihoazobenzOi -.

-; The water-soluble fieafctlv used according to the invention Dyes can be used as fiber-reactive radicals, e.g. the following tints Having residues and substituents

Chlörmaieinyläiriiriogruppen, the Pröpiöl groupingi Möno-DiöMötfeirötunyiaMnögPüppeft, Bromine "- or Ghiöracrylantino-

i Acrylamino groups, Vinylsiiifori groups and which contain unstable substituents Which are easy to take away with the pair of binding electrons are e.g. aliphatic bound sulfuric acid or fiiiösoht'öföläurestergruppen and aliphatically bonded Sulfonyl * or sulfonyloxy groups or halogen atoms, in particular an aliphatically bound chlorine atom * These unstable substituents are expediently in α- or 0-gteliiing o an aliphatic radical which has a ite - or Ämittosulfohylgt * iippe to the dye-

is bound; at those in question Dye> the Halogettatölme as labile substituents These exchangeable halogen atoms can also be contained in them e.g. in tiiiem Aoetyirest or in α- and ß-position one Propionylrestes stand. Examples of such radicals are, for example, chlorine or α, β-dichloro or dibromopropionylamino groups or α-chloroacetylaraino groups. Preferably however, the halogen atoms which can be split off are located in a preferably 2 to 3 ring heteroatoms, in particular Ring nitrogen atoms .containing heterocyclic radical,.,

⁽ BAD LOCATIONQINAL.

2520295

e.g. in a Phthaiazin-, Pyridaüin-, Pyridazori-, Chihoxaline, quinazoline> oxazole; Thiaz oil, especially but in a pyrimidine or especially triazine ring, e.g. in a grouping of the formula

N
Halogen *

wherein Z is a hydrogen atom, an optionally substituted amifto group, an etherified oxy or mercapto group or represents a halogen atom or an alkyl, aryl or aralkyl group. The halogen atoms are e.g. bromine, atoms, but preferably chlorine atoms. Of particular interest is the use of dyes, which the grouping of the formula

contain, in which 25 * a Ghlöratom, a ^v NHg group or the

A residue of an äliphatisohen or aromatic amine means:!

also those fiber-reactive groups whose removable ones:

öubstitwent one in particular to a carbon atom ^; ί

of a heterocyclic radical bound 'quaternary ammonium'

öavr Hydrasinii'.mgruppö represents, ci'.h. a group of; _

BAD ORiGiMAL

0 0 9 Q 4 7/1 7 7 7

N-C

or -NiM ^ f S

k'ei

wherein Z ₂ denotes a hydrogen atom, an optionally substituted amino group or a etherified oxy or xercapto group.

The dyes to be used according to the invention are known in large numbers. They can be prepared by methods customary per se, for example by acylating dyes of the most varied classes containing primary or secondary amino groups, but in particular of the anthraquinone, phthalocyanine or azo group acylating agents which contain one or more reactive groups. as such acylating agent £ .B are. the anhydrides or chlorides of the corresponding the above-mentioned aliphatic acylamino acids, for example of acrylic acid, propiolic acid, chloromaleic acid, Chloracryisäure, α, β-dibromopropionic acid _r ß-Chlorpropionylsäure etc., but above all, the heterocyclic reactive radicals corresponding halides, dhz3 called the following:.

2-Kaloger / oenzthiazol- or -oxazolcarbon- or -sulfonsäurechlorid, · "·

ORIGINAL 009847/1777

^, o-dichloropyridazine-S-carboxylic acid chloride,
Tetrachloropyridazine, '..

4, ^ - Dichlorpyricazon- (6) -yl-propionic acid chloride,
^, S-dichloro-l-phenylpyridazon-carbon- or -sulfonic acid- · ■ chloride,

4, S-dichloropyridazonopropionic acid chloride,
1,4-dichlorophthalazine carbon or sulfonic acid chloride, 2,3-dichloroquinoxaline carbon or sulfonic acid chloride, 2,4-dichloroquinazoline carbon or sulfonic acid chloride, 2,4,6-trichloro- or 2,4,6-tribromopyrimidine and their derivatives, which e.g. in the 5-position a cyano, nitro,
Methyl, ethyl, carbamide, sulfamide, carbomethoxy, carbalkoxy, acyl (e.g. benzoyl, acetyl or propionyl), alkenyl (e.g. allyl or chlorovinyl), or a substituted alkyl ( Carboxy-methyl, chloromethyl or broramethyl) groups, for example. 2,4,5,6-tetrachloro- or 2,4,5,6-tetrabromopyrimidine,
2,6-dichloro- or 2,6-dibromo-4-carboethoxypyrimidine, - '. ~ 2,4, S-trichloropyrimidine,
5-nitro-6-methyl-2,4-dichloropyriinidine,
2,4-dichloropyrimidine-6-carboxylic acid chloride,
2,4-dichloropyrimidine-5-carboxylic acid chloride,
. 2,6-dichloro- or 2,6-dibromopyrimidine-4- or -5-carboxamides or sulfonic acid amides or
-4- or -5-carboxylic acid or sulfonic acid chloride,
2,4-dichloropyriidine-5-sulfonic acid 3,

009847/1777

2, ² T-di bromo-p-bromo-r.etfcyl-o-methylpyrimidine,

2,5,6 ~ richlor-4-methylpyrirnidine,. '

2,6-D'ichlor-ty-triöhlörmethylpyrimidin or in particular

or * ^, ^, ej ^^

-I ^ Ji 5-triazines, which are substituted in .2.-position by an aryl or alkyl radical, for example a phenyl, methyl or ethyl radical, or by the radical of an aliphatic or aromatic, via the sulfur atom .. bonded mercapto or hydroxyl compound bonded via the oxygen atom, or in particular through an -NH ^ group or through the residue of an aliphatic, heterocyclic or aromatic amino compound bonded via the nitrogen atom. Such compounds, the radicals of which can be bonded to the triazine nucleus in the 2-position by reaction with trihalotriazines, include the following selenium: aliphatic or aromatic mercapto or hydroxy compounds, such as thioalcohols, thioglycolic acid, thiourea, thiophenols, methyl, ethyl , Isopropyl alcohol, glycolic acid, phenol, chloro- or nitrophenols, phenolecarboxylic and sulfonic acids, maphthola, naphthol sulfonic acids, etc., Insbö &onduc'ö but · '003847/1777

BATH ORIGINAL

Ammonia and acyliorbare AfSinögrupper. Essential compounds such as hydroxylamine, hydrazine,? Hör.ylftydrazine, phenylhydrazine sulfonic acids, carbamic acid and their? Derivatives, semi- and 3? Hioaesvi carbazide and carbazones, methyl-, ethyl-, isopropyl-, foethöxyethyl-, methoxypropylamine, dimethyl-, Öiäthyi-, Meshyiptienyl-, 'phenylamine, Chloräthyiaaiin, Ethatiolämine, Pröp Sönzylamin, Cyclohexylamin, Cyclohexylamin, Cyclohexylamin, Cyclohexylamin, Cyclohexylamin, fiperidine, piperazine, Afflittökohlensäureesuei *, Äminöessigsäüreäthylestser, Aminöäthansulfonsäurö, N-Methyiainir.oathar.sulfonsäure, but above all aromatic amines, such as aniline, ji-methylaniline, toluidines, aminopetaniline, aminopetaniline, aminopetaniline, p- Nitrotoluidines, phenylenediamines, tolylenediamines, anisidine, phenetidine, diphenylamine, naphthylamine, aminonaphthols, diaminonaphthalenes and, in particular, anilines containing acidic groups, such as sulfanil, metanil ,. Orthanilic acid, aniline disulphonic acid, aminobenzylsulphonic acid, aniline, (O-methanesulphonic acid, aminodibenzoic acid, naphthylamine mono-, di- and trisulphonic acids, aminobenzoic acids such as 1- or S-oxy-S-aminobenzoic acid, aminonaphthonic acids and -tr, -disulphonic acids , Aminobenzoic acid sulfonic acid etc., also colored compounds, or compounds with dye character, ^{e.g. 1} I-Xitro-V-aminosfcilbendisulfonsäure and A ;; ilnoa ^ ofarbuwo: Tü der Air.inoanthrachinona or Pht; - .. iloc: y- ; :: U; ie, di

009847/1777

SAD ORIGINAL

at least one reactive amino group contain. :

The introduction of the in 2 position by the rest eir.er hydroxyl, mercapto or amino compound or A.T ..- noniak substituted trlazine residues can be expedient also done in such a way that one in the ghlortriazine dye produced by condensation Halogen atom replaced by reaction with one or different of the above-mentioned compounds.

Furthermore, you can in the dyes prepared as indicated, which have a ß-chloropropionyl, α, β-dichloro or Dibro.T.propionylrest, these subsequently According to the invention by splitting off hydrogen potassium by means of alkaline reacting agents into an unsaturated one Acyl radical, e.g. 3. convert an acrylic, chlorine or bromoacrylic radical.

COPY 009847/1777

The water-soluble fiber-reactive dyes which are used according to the present invention can also have the following fiber-reactive groups: 2-i ^v »ethylthio-4-fluoropyrimidine-5-carbonyl-, 2,4-bis- (phenylsulfonyl) -triazinyl- 6-, 2- (5'-carboxyphenyl) -sulfonyl-4-chlorotriazinyl-6-, 2- (3'-sulfophenyl) -sulfonyl-4-chlorotriazinyl-6-, 2,4-bis (jj'-carboxyphenyl -sulfonyl-l ^ -triazinyl-6- ,, 2-carboxymethylsulfonyl-pyrimidiny1-4-, 2-methyl-sulfonyl-6-methyl-pyrimidinyl-4-, 2-phenylsulfonyl-6-ethyl-pyrimidinyl-4-, sio-bismethylsulfonyl -pyrimidinyl-ö-, 2,6-bis-methylsulfonyl-5-chloro-pyrimidinyl-4-, a ^ -Bis-methylsulfonyl-pyrlmidinyl-S-sulfonyl-, 2-methylsulfonyl-pyrimidinyl-4-, 2-phenylsulfonyl- pyri-

• j 'midinyl-4-, 2-trichloromethylsΰlfonyl-6-methyl-pyrimidinyl-4-, \

2-methylsulfonyl-5-chloro-β-methylpyrimidinyl-4-, 2-methylsulfonyl * j

. Ί 5-brora-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-6-ethyi- '' (pyriraidinyl-4-, 2-methylsulfonyl-5-chloro-6-chloromethyl-pyriraidinyl- ■ 4 -, 2- ^ ίethylεulfonyl-4-chloΓ-6-raethylpyriInidin-5-sulfonyl-, ■ 'j

2-methylsulfonyl-5-nitro-6-raethyl-pyrimidiny1-4-, 2,5,6-trisniethylsulfonyl-pyrimidinyl-4-, 2-methylsulfonyl-5,6-diraethyl-,. pyrimidinyl-4-, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4, ' 2-Kethylsulfonyl-6-chloro-pyΓimidinyl-4-, 2,6-bis-methylsulfonyl- S-chloro-pyrimidinyl - ^ -, 2-methylsulfonyl-6-carboxy-pyriraidinyl-4-, 2-methylsulfonyl-5-sulfo-pyriinidiny 1-4-, 2-methylsulfonyl-6-!

carboraethoxy-pyrimidinyl-4-, 2-Kethylsulfonyl-5-carboxy-pyrimidi-

nyl-4-, 2-methylsulfonyl-5-cyano-6-methoxy-pyriraidinyl-4 · p ,. 2-yiethylsulfonyl-5-chloΓ-pyriraidinyl-4- _/ 2-sulfoethylsulfonyl- ί

• 009847/1777 ORiG ₁ NAL, nspected

o-methyl-pyrimidinyl-4-, 2-ketiaylsulphonyl-5-b2 * om-pyrimidinyl- ^|: l-,

S'-phenylsulfonyl-S-chloro-pyrimidinyl- ¹ ! -, 2-carboxymethyl- .j

sulfonyl-5-chloro-6-ni: ethyl-pyrimidinyl-4-, 2-methylsulfonyl-6-. chloro-pyrimidine - ^ - and -5-carbonyl-, 2,6-BIs- (rr.e · thy lsulfony I) -pyrimidine-4- or "-S-carbonyl-, ^ -ethylsulfonyl-ö-chloropyrirnidine-5 -carbonyl-, Z ₃ 4-bis- (methylsulfonyl) -pyrimidine-5-sulfonyl-, ^ -mothylsulfonyl- ^ chloro-o-methylpyrimidine ^ -sulfonyl or -carbonyl , ^ -. chlorobenzothiazole-S- or -β-carbonyl - or -5- or -6-sulfonyl-, 2-arylsulfonyl- or 2-alkylsulfonylbenzthiazole-5- 'or -6-carbonyl- or -5- or -β-sulfonyl,;

such as 2-methylsulfonyl- or ^ -Eethylsulfonyl-benzothiazole-S- or -6-sulfonyl- or -carbonyl, 2-phenylsulfonyl-benzefehiazole-5 "or -6-silfonyl- or -carbonyl- and the corresponding derivatives of 2-sulfonylbenzth: iazole-5- or -β-carbonyl- or -sulfonyl- which contain sulfo groups on the fused benzene ring, such as 2-chlorobenzothiazole-5- or -β-carbonyl- or -sulfonyl, ^ -chlorobenzimidazole-S - or -β-carbonyl- or -sulfonyl-, 2-chloro-1-methylbenzimidazole-5- or -β-carbonyl- or -sulfonyl-, ■ 2-chloro-4-methylthiazole-Cli3) -5-carbonyl- or -4- or -5-sulfonic '* fonyl residues and the N-Öxyd of chloro- or 4-I \ fitrochinolin-5- · carbonyl-Hestes. Mention may be further 2 ₄ 2,3j3-Teträfluorcyclobutancarbonyl-l- or -sulfonyl - *! -, .2

difluorcyclobutane-l-carbonyl-And ^ - (^, S ^

biityl-l) -acryloyl-, α- or ß-Bx'omacryloyl- and ar oägr ß »alkyl-

or -arylsulfonylacryloyl residues. ' ■ ^

ORIGINAL INSPECTED '.

0.09.8 47 / 17TT '*,. .

2020235 : - 26 -

According to the invention, the metal complex dyes are used preferably those of the dispersion series, which one? as Heavy metals contain iron, cobalt, nickel, chromium and copper in complex bonds.

As such disperse complex dyes are especially azo dyes in question, those in non-metallized

State a group of the formula

X,

contain, in which X, and Xp = -OH, -NHp., -NH-R, and --- "X-OH. Particularly important are dyes that contain atom groups of the formulas in the ι · α ~. call-free state

HH ₀

^c H-Q

or OH

i H—

-— -A. -7

• t-K \

<'. rvlihal IeIi ₁₁

0847/177 7 bad original

- ■ 27 -

Examples are the cobalt and chromium complexes of the following dyes (R = -NHp, -alkyl, -NH-alkyl, -N (alkyl) ₂ ; the arrows indicate the direction of coupling):

COOH

R-SO ₂ ^ C> NH, pyrazolone

OH

R-SO ₂

OH R-S0 "- <> NH

₂ <_> NH ₂ (Cl) pyrazolone

2-naphthol

1-acylamino-7-naphthol

Pyrazolone
2-naphthol

OH

R-SO,

H, 4-methyl-6-nitro-2-aminophenol 4-nitro-2-ainophenol

NH,

R-SO

2
OH

R-SO

2
OH

SO ₂ R 4-chloro-2-aminophenol 4-chloro-5-nitro-2-aminophenol

5-nitro-2-aminophenol

4-nitro-2-aminophenol

1717

as well as the following complex dyes

OH OH

0J- ( } —N = N— \ y copper complex and nickel complex

HO

OH

N = N-e

COOK

OH

-N = N-C.

HO
^ CN

C = N

I.

Copper complex

Copper complex

Also suitable are complex dyes of the phthalocyanine series and the 1,5-diarylformazan series which are free from sulfo groups.

The quaternized to be used according to the invention .Dyes contain at least one quaternary nitrogen atom, which is either aliphatic, cyclic or from structural type of the quinone imine, i.e. it is bound directly to the aromatic ring.

The customary salts and metal halide, for example zinc chloride double salts are preferably used the known cationic dyes, in particular the methine or. Azamethine dyes that denote the indolinium, pyrazolium, imidazolium, triazolium, tetrazolium, oxdiazolium, thiadiazolium, Oxazolium, thiazoliura, pyridinium, pyrimidinium,

η η α π /. ί 1 1 ^{ ϊ ι * ι

Pyrazinium ring included. The heterocycles mentioned can be substituted and / or condensed with aromatic rings. Furthermore, cationic dyes of the diphenylmethane, triphenylmethane, oxazine and triazine series are also possible finally also colored salts of the arylazo and anthraquinone series with external onium group. For example, the dyes of the formulas are mentioned:

Cl

CH.

CIL

CH ₀ CH ₀ OH

CiL

ZnCl,

HC JSF-CH

Il Il

N C- ^ I =

CH ₃

ZnCl.

HCl

() () ■) a ■ '► 7 Ί77 7

C.I. Basic Yellow 13 (OIL) N-

.Cl "

Λ- COOC ₂ H,

Λ — ο (οη ₃ ) ₂
C-CH = CH- CH ₀
"O < ² OH ₂ 01 I. XiH., CH

Cl

Οϋ., Η, -I el b

■), 1

ORIGINAL IMSPECTED

(;. · ■■ ··: '' 'M 77

- 31 -

Cl CH,

Cl '

-N (

HSO,

0-- -NH

EnCl.

O ₂ N

-CN = NC = NN = ¹ «II , N-CH ₃ CH ₃ N

CH, CH

ZnCl,

ft η η 1 1 / γι s * re * ft

NH,

₀ 2

3 3

NH, CH ₃ OSO ₃ "

Cl

Cl

N = N. CH ₃ OC i ^ -N = ^N

OCH,

N (C ₀ Hj

2 "5'2

Cl

and their mixtures.

ft Π Q ß /. Ί

Among the acidic nouns dyes are especially those that differ from benzidine, Practice diaminost and dehydrothiotoluidine as diazo components, derive. Coupling products of 6-amino-1-naphthol-3 "sulfoic acid and condensation products are also of importance from two aminoazo dyes with phosgene or Cyanuric chloride,

The salts of the dyes containing sulfo groups with aliphatic primary, secondary and tertiary are also used Amines of the fatty series, such as dodecylamine, are in question.

Metal complex dyes free of sulfo groups are conducted mainly from azo dyes, in which two to the Substituents capable of complex formation especially hydroxy, Carboxyl groups or cyclically bonded nitrogen atoms either in the ortho- or peri-position in an aromatic or heteroaromatic radical or else in the ortho positions V two aromatic or linked by an azo bond heterocyclic radicals are located. Furthermore are the metal complexes called by formazan dyes, in which the two to Groups capable of complex formation in the ortho positions of two linked by a 1,2,4,5 ~ tetrazapentamethylene chain aromatic or heteroaromatic radicals are located.

ORlGINALiNSPECTED

ΊΊ1

Optionally additionally usable solvents which are added to the phosphorus derivative can, for example, the hydrophobic solvents which are immiscible or only partially miscible with water, such as acetophenone, Cyclohexanol, benzyl alcohol, esters such as ethyl acetate, propyl acetate, butyl acetate, hydrocarbons, such as benzene, xylene or toluene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, trichlorethylene, perchlorethylene, trichloroethane, Tetrachloroethane, dibromoethylene or chlorobenzene.

Water-miscible, hydrophilic solvents form a particularly preferred class of solvents, such as, for example aliphatic alcohols such as methanol, ethanol, n-propanol, isopropane oil, ketones such as acetone, methyl ethyl ketone, Cyclohexanone, ethers and acetals such as diisopropyl ether, diphenylene oxide, dioxane, tetrahydrofuran, glycerol formal and glycol formal, as well as acetonitrile and pyridine, diacetone alcohol ", as well as higher-boiling glycol derivatives, such as Ethylene glycol monomethyl, ethyl and butyl ether and Diethylene glycol monomethyl ether or ethyl ether, thiodiglycol, polyethylene glycols, as well as at room temperature are liquid, ethylene carbonate, 7-butyrolactone and especially the group of water-miscible active solvents such as N, N-dimethyl-

■ / 7 7

formamide, Ν, Ν-dimethylacetamld, bis- (dlmethylamido) -methanphosphafcy Tris (dimethylamido) phosphate, -. N-methyl pyrrolidone, 1,5-dimethylpyrrolidone, Ν, Ν-dimethyl-methoxyacetamide, Ν, ^, ΝΓ, Ν'-tetramethylurea, tetramethylene sulf on (SuIfolan) and 3-Methylsulfolan and Dimethylsulfoxyd.

The dye preparations according to the invention can Contain dispersants. For water-soluble dyes the addition of dispersants is not necessary if the preparation to a mainly of water or water be given as a discrete phase containing dye liquor target. Likewise, the use of dispersants can optionally be dispensed with, if water-insoluble dyes to be dissolved in an organic liquor. In In other cases, namely whenever the dyes are at least partly present in the dispersed state in the dye liquor, there is the presence of dispersants displayed.

Important representatives of such dispersants belong in particular to the following non-ionic compound types: a) Polyglycol compounds such as polyoxyalkylated fatty alcohols, polyoxyalkylated polyols, polyoxyalkylated mercaptans and aliphatic amines, polyoxyalkylated alkylphenols and

Π Π 9 R L. ? / 1 1 Ί 7

-naphthols, polyoxyalkylated alkylarylmereaptanes. and Alkylarylamines.

b) Fatty acid esters of ethylene and polyethylene glycols, as well as propylene and butylene glycol, of glycerol or the polyglycerols and pentaerythritol, and sugar alcohols such as sorbitol, sorbitans and the Sucrose. .

c) N-hydroxyalkyl carbonamides, polyoxyalkylated carbonamides and sulfonamides.

d) Liquid polyalkylene glycols, especially polyethylene glycols.

Examples which may be mentioned as advantageously usable dispersants from these groups are: adduct of 8 moles of ethylene oxide with 1 mole of p-tert. Octylphenol, from 15 or 6 moles of ethylene oxide to castor oil , from 20 moles of ethylene oxide type the alcohol C, gH, OH, ethylene oxide. Addition products of di- (a-phenylethyl) phenols, polyethylene oxide tert-dodecylthioether, polyamine, polyglycol ethers or addition products of 15 or JO moles of ethylene oxide with 1 mole of amine C ₁₀ H ₀₁ -NH ₀ or C ₁₀ H ^ JIH ₀ .

Ld dr) d Io j (d

Particularly valuable dispersants are sodium sulfosuccinate, sodium alkyl aryl sulfonates, amin-alkyl aryl sulfonates, Fatty acid esters of sorbitan, ethoxylated alkanolamides, ethoxylated phenols and ethoxylated Phosphate R t he »

ft fi Q ß L Ί / 1 ^ '/ Ί

The present preparations must not be used at the same time

a) Dyes in which there are primary, secondary or

are / tertiary basic nitrogen atoms / and contain an amount of an acid which is at least equivalent to the nitrogen atoms. ■ .- ■■■ -. ■ ·. ■

The production of the dye preparations according to the invention is usually done by simply mixing, stirring expediently, or by grinding the Components e.g. in a ball mill.

The dye preparations described above are suitable for the preparation of conventional aqueous Dye baths and especially for the production of dye baths based on organic solvents in which the dyes are dispersed or preferably dissolved. . In the following examples, the parts unless otherwise indicated, parts by weight that Percentages by weight, and temperatures are in Degrees Celsius ■ indicated.

ORIGINAL INSPECTED

Example 1.

2 parts of an antraquinone dye of the formula

COO Il

0 NH- (CHg) ₅ -N (CH ₅ )

3 parts of hexamethylphosphoric acid triamide and 1 part of an adduct 5 moles of ethylene oxide on rinus oil are finely ground in a ball mill. One receives a low-viscosity dye preparation which, when added to a foulard liquor made of tetrachlorethylene, increases immediately distributed in a homogeneous solution.

.1 M ■ ".

Example 2.

10 parts of a fiber-reactive disperse dye the formula

BrCHg-CHBr-CO-Ni

are in a well-stirred mixture of 10 parts of Hexamethyli hoi5phoramid and 2 parts of sorbitan monolaurate. entered and stirred for so long, Mc a clear solution has arisen, from which no dye crystallizes out even on cooling to -10.

If you leave the dispersant (sorbitan monolaurate) away, you also get a clear preparation.

η ι η s

- 40 Example 3.
Parts of the acidic wool dye of the formula

N = N

SO, "K ⁺

are stirred into 30 parts of hexamethylphosphoramide registered. The mixture is stirred for 2 hours at 35 to 40 °, the Dye goes into solution. It is then cooled to 10 °, 10 parts of triethylene glycol monomethyl ether are added and filtered from small amounts of salt. A thin, clear dye preparation is obtained.

Further dye preparations, which according to the Details of Examples 1 to 3 are obtained are listed in the table below.

0384 7/1177

ο J ο af CD

ι ■. ■ ■

j dye / parts

:

C.I. Basic Yellow 15 ^ (as acetate) 20 parts

G.I * Acid Orange 3

(als.K-SaIz) 2 parts

C.I. Solvent Yellow 2.

Part 1

Cl

NC

33 parts

C ₉ H,

OCH, CH,

30 parts of solvent.

Hexame thylpho spiiortriamid 15 parts

Ethylene glycol monomethyl ^ ether

15 parts

Hexamethylphosphoric triamide

2 parts
Pyridine 1 part

Hexaraethylphosphorus triafflid

1 part SuIfοlan 1 part

Hexame thylphos phortriamid . 67 parts

Hexamethylphosphoric triamide 40 parts

Dispersants

CD JSJ

Addition product of 40 moles of ethylene oxide on castor oil

'.30 parts

Dye / parts

CI. Direct Red 3 parts'

• Ν-

20 parts

C.I..Basic Blue 3.8 parts

HO

33 parts

C.I. Acid Orange (Potassium Salt) 2 parts J solvent

Hexamethylphosphoric triamide 5 parts

Diethylene glycol monomethyl ether

3 parts

Hexamethylphosphoric triamide 65 parts

Hexamethylphosphoric triamide 6.2 parts

Hexamethylphosphoric triamide 67 parts

Hexamethylphosphoric triamide 3 parts

Dispersants

Tri ethanol ammonium salt of coconut fatty acid

Part 1

Sodium oleate 15 parts

Coconut fatty acid ethanolamide j Part 1

! Dye / parts

Cl

CJLOCOCH, 2 4

CN

HN

Cl

[12

I.

2.3 parts

OC ₂ H ₄ OC ₂ H ₅

! I C-O

Il

-N

Parts

NO,

NHK3

SO ₀ NHC ₅ H-Cl 2

Parts

solvent

Hexamethylphosphoric triamide
7.7 parts

Hexamethylphosphoric triamide 50 parts

Hexamethylphosphoric triamide

5 parts

Tetrachlorethylene 10 parts

Dispersants

Addition product of 9 moles of ethylene oxide with nonylphenol

25 pieces

Stearyl alcohol + 20 moles of ethylene oxide

5 parts

I dye / parts

OH

2 parts solvent

Hexamethylphosphoric triamide

Parts

Dispersants

HN (C ₂ H ₄ OH) ₃

Parts

Claims (1)

1. Dye preparations, characterized in that they a) a dye, b) a solvent which is a phosphorus derivative, and c) optionally a dispersant, d) optionally a further textile auxiliary and e) optionally a further solvent contain. 2. Dyestuff preparations according to claim 1, characterized in that they are hexamethylphosphoric triamide as the phosphorus derivative contain. 5. dye preparations according to claims 1 and 2, characterized in that they contain at least 20, preferably 25 to 50 $ dye, based on weight of the finished preparation. 4. Dyestuff preparations according to claim %, characterized in that they contain only the phosphorus derivative as a solvent. 5. dye preparations according to claim 5, characterized in that 009847/177 7 indicates that they do not contain a dispersant. 6. dye preparations according to claims 1 to 4, characterized by having up to $ .50 of the existing Phosphorus compound are replaced by the dispersant. 7. dye preparations according to claim 6, characterized in that that they contain a non-ionic dispersant. 8. dye preparations according to claim 6, characterized in that that they contain an anionic dispersant. 9. dye preparations according to claims 1 to 8, characterized in that they contain a dye free of sulfo groups. 10. Dyestuff preparations according to claim 9 *, characterized in that that they contain a disperse dye. 11. Dyestuff preparations according to claim 10, characterized in that that they disperse dyes, hexamethylphosphoric triamide and dispersants anionic and / or 9847/1777 non-ionic type. 12. Dyestuff preparations according to claim 11, characterized in that indicates that they do not contain any free acids. 15. Paraffin preparations according to claim 9, characterized in that they contain at least one quaternary Contain nitrogen atom containing dye. 14. Dyestuff preparations according to claim 13 »characterized in that that it is also a leveling agent for dyeing acrylic fibers with quaternized dyes exhibit. 15. Dyestuff preparations according to claim I ¹ J, characterized in that they contain an anionic or a cationic leveling agent. . 16. Dye preparations according to claim 9, characterized in that they contain a metal complex dye, 17. Dyestuff preparations according to claim 9 * characterized thereby, that they have a paint-soluble or for that BAD ft ft β / ι / η π * ί Dyeing of cellulose acetate spinning pulps contain suitable dye. 18. Dyestuff preparations according to claims 1 to 8, characterized in that they contain a sulfo group-containing dye. 19. Dyestuff preparations according to claim l8, characterized in that that they have an acidic nylon dye or Contain wool dye. 20. Dyestuff preparations according to claim l8, characterized in that that they contain substantive cotton dyes. 21 "Color stains" prepal ite_according to claim 18, characterized in that that they contain an acidic fiber-reactive dye » 22. Dye preparations according to claims 1 to 8, characterized in that they simultaneously a) a water-insoluble disperse dye and b) a water-soluble contain acidic, fiber-reactive dye. ORIGINAL INSPECTED 009847/177 7 25. Process for the production of the dye preparation © according to claims 1 to 22, characterized * that components a3 and b), "and if available, c) and d), mixed. . , - ■. "'■ 24. Process for the manufacture of dye preparations according to claim 23, characterized in that the Components a) and b) either alone or, if present, married with components c) and d). 25. Method zur.Herstellung of dye liquors, thereby characterized that one the dye preparations used according to claims 1 to 24. ■ 26. Process for ^ Hfers-feellr by gekennze ^ iahHetTT ^^ one asserts the dye preparations according to claims 1 to 24 with an organic solvent, with an aqueous liquor, or with an emulsion of both mixed. ·