DE2033253A1 - Dyes. Process for their production and their application - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 6818 / E ■

Germany

Dyes, processes : their manufacture and their application . "

The present invention relates to new, valuable dyes which are free from water-insoluble acid groups and which contain at least one fiber-reactive radical Z bonded to an araino group with at least one fluorine atom. Tuted nitrogen-containing heterocycle, '' but in particular-contain one with at least one Pluorafco® s-triazine residue. B & aenaeva ■ int @ ressax & § si dyes nit '·

. "'..' ■ ■ '.00-9883 / 19Ig' '· ■"

the s-triazine radicals Z of the formula

where one X is a fluorine atom and the other X is an organic radical,

a

such as a hydrocarbon radical in particular / alkyl or aryl radical, is an amino group or a halogen atom. Preferably, one X is a fluorine atom and the other X is a chlorine atom or, in particular a fluorine atom.

Preferred residues Z are flalogenatom with only one of the 2-fluoro-4-amino-6-triazinyl, 2-fluoro-4-methylamino-6-triazinyl- _j> 2-fluoro-4-phenylamino-6-triazinyl, 2 -Fluoro-4-diethyl-amino-6-triazinyl-, 2-fluoro-4-methoxy-6-triazinyl-j, 2-fluoro-4 (β-methoxyethoxy) -ö-triazinyl-, 2-fluoro- ¹ I-PhBnOXy-O-triazinyl-, 2-fluoro-4-ethoxy-6-triazinyl-, 2-fluoro-4-methylmercapto-6-triazinyl- _i 2-fluoro-4-pheny1-6-triazinyl-, 2- Fluoro-4-methy1-6-triazinyl and 2-fluoro-4-ethyl-6-triazinyl radical _o

These are the alkyl, phenyl and alkoxy-fluorotriazinyl radicals particularly preferred »

The invention relates, for example, to azo dyes, in particular mono- and disazo dyes, anthraquinones, "perinones ^ quinophthalones, styryl dyes and nitro _{dyes o} azo dyes ^

Especially ueen intersssaafcta dyes include "

QP ß> <3) f) q 0 [5 0i

a e a θ i /! 9 g ö

the monoazo dyes of the formula

wherein D is the radical of a diazo component., Ä is an arylene radical, ins-. particular an optionally substituted 1,4-phenylene radical, R. and Rp each an optionally substituted alkyl group, where at least one of the radicals D, A, R ^ and R _? contains a fiber-reactive radical Z, where Z stands for the fluorinated triazinyl radical defined above. -.

The diazo radical D is mainly derived from mono- or bicyclic amines of the formula D-NH ₂

such as any diazotizable heterocyclic amines which contain no acidic water-solubilizing substituents, but in particular amines which have a heterocyclic five-membered ring with 2 or 5 heteroatoms, especially one nitrogen and one or two sulfur, oxygen or nitrogen atoms as heteroatoms, and aminobenzenes , especially those of the formula _a

wherein a is a hydrogen or halogen atom, an alkyl or alkoxy, phenoxy, nitro, cyano, carbalkoxy or alkylsulfone group, b is a hydrogen or halogen atom, an alkyl, cyano or trifluoromethyl group and c ^! a nitro, cyano, carbalkoxy

009883/1958

Sulfonsäureamld- or AlkyIsulfony1gruppe mean.

Examples of such amines are: 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-5-methylsulfonyl-thiazole, 2-amino-5-cyanthiazole, 2-amino-4-methy1-5-nitrothiazole, 2 -Araino-4-methylthiazole, 2-amino-4-phenylthiazole, 2-amino-4-p + '- chloro) -phenylthiazole _JI 2-amino-4- (4'-nitro) -phenylthiazole, 3-aminopyridine, 3- Aminoquinoline, ^ -aminopyrazole, 3-amino-1-phenylpyrazole, 3-aminoindazole, 3-amino-1, 2, 4-triazole, 5- (methyl-, ethyl-, phenyl- or benzyl-) - 1,2, 4-triazole, 3-amino- ^{1- (4!} -Methoxyphenyl) pyrazole, 2-aminobenzothiazole, 2-amino-6-methylbenzthiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-chlorobenzothiazole, 2-amino -6-cyanobenzthiazole ₁ , 2-amino-6-thiocyanobenzothiazole, 2-amino-6-nitrobenzthiazole,

009883/1958

2-Aπlino-6-car.boethoxybenzthiazole ·.

2-amino- (4- or 6-) methylsulfonylbenzthiazole, 2-Amino-lej5,4-thiadiazole 2-Amino-l, j3. " 5-thiadiazole 2-Amino-4-phenyl- or -4-methyl-l ^, 5-thiadiazole, 2- Amino-S-phenyl-l ^ j-thiadiazole 2-amino- / 5-nitro-5-methylsulfonylthiophene, 2-amino-3i5-bis (methylsulfonyl) thiophene, 5-amino-5-methyl-isothiazole 2-amino-4-cyano-pyrazole,

2- (4'-Mtrophenyl) -3-amino-4-cyanopyrazole,

3- or 4-aminophthalimidj aminobenzenes
l-amino-4-chlorobenzenes l-amino-4-bromobenzene, l-amino-4-methylbenzenes 1-amino-4-nitrobenzene, l-amino-4-cyanobenzene, l-amino-2e5-dicyanobenzene, 1-amino 4-methylsulfonylbenzenes l-amino-4-carbalkoxy benzene, l ~ amino-2, ^ - dichlorobenzene,

l-Amino-2e4-dibromobenzenes l-Amino-2-methyl-4-chlorobenzenes l-Afflino-2-trifluoromethyl-4-chlorobenzene, l-Amino-2-cyano-4-chlorberizole _>

009883/1953

1-amino-2-carbomethoxy-4-chlorobenzene, 1-amino-2-carbomethoxy-4-nitrobenzene, 1-amino-2-chloro-4-cyanobenzene _J 1-amino-2-chloro-4-nitrobenzene, 1- Amino-2-bromo-4-nitrobenzene, 1-amino-2-chloro-4-carbathoxybenzol, 1-amino-1-chloro-4-methylsulfonylbenzene, ) 1-amino-1-methylsulfonyl - 4-chlorobenzene, 1-amino-2-methylsulfonyl -4-nitrobenzene, l-amino-2 _J 4-dinitrobenzene, 'l-amino-2,4-dicyanobenzene _i l-amino-2-cyano-4-methylsulfonylbenzol, 1-amino-2,6-dichloro-4- cyanobenzene, l-amino-2,6-dichloro-4-nitrobenzene, l-amino-2j 4-dicyano-6-chlorobenzene, 4-aminobenzoic acid cyclohexyl ester, l-amino-2,4-dinitro-6-chlorobenzene and in particular l-Amino ^ -cyan ^ -nitrobenzene, also l-aminobenzene-2-, -J> - or -4-sulfonic acid amides, such as η-methyl or Ν, Ν-dimethyl or diethylamide, N> 7-isopropyloxypropyl -2-amino-naphthalene-6-sulfonic acid amide, N, 'y-isopropyloxypropyl-1-aminobenzene-2-, -> - or -4-sulfonic acid amide,

N-isopropyl-l-aminobenzene-2-, -J- or -4-sulfonic acid amide, N, 'Y-methoxypropyl-l-aminobenzene-2-, - ^ - or -4-sulfonic acid amide N, M-bis (ß- hydroxyethyl) -l-aminobenzene-2-, -3- or -4-sulfonic acid

009883/1958

amide,

l-Amino - ^ - chlorobenzene ^ -sulphonic acid amide, and the N-substituted derivatives, 2-, 3- or 4-aminophenylsulphamate, 2-amino-4 ~, -5- or -6-methylphenylsulphamate,
^ -Amino-S-methoxy-phenylsulfamate,

^ -Affiino-ö-chlorophenyl sulfamate, ■

3-Amino-2 _J 6-diclilorphenylsulfamat, 4-Amino-2- or -jj-methoxyphenylsulfamat, N, N-Dimethyl-2-aminophenylsulfamat, NjN-Di-n-butyl-2-aminophenylsulfamat, N / N-Dimethyl ^ -amino- ^ chlorophenylsulfamate, N, n-propyl-2-aminophenylsulfamate, N _J N-di-n-butyl-3-aminophenylsulfamate _> 0 (3-aminophenyl) -N-morpholine-N-sulfonate, 0 (3-aminophenyl ) -N-piperidine-sulfonate, N-cyclohexyl-0- (3-aminophenyl) -sulfamate, N (N-methylaniline) -0- (3-aminophenyl) -sulfonate, NjN-diethyl-I-amino-O-methylphenyl -sulfaniat, N-Aethylenimin-0- (4-aminophenyl) -sulfonat, NiN-Dimethyl - ^ - aminophenylsulfainat, "

0 (n-Pröpyl) -0 (3-aminophenyl) sulfonate, 0, ß-chloroethyl-Ö (2-aminophenyl) sulfonate, 0-benzyl-0 (3-aminophenyl) sulfonate and O-Ethy 1-0 (4-amino-2,6-dimethyl-phenyl) sulfonaite. '

4-Aminoazobenzenes which can be used as diazo components are, for example, 4-aminoazobenzene, 4-amino-2-nitroazobenzene _;

009833/195 8 ■

3,2'-dimethyl-4-aminoazobenzene,

2-methyl-5-methoxy-4-aminoazobenzene *

2,5-dimethoxy-4-aminoazobenzene,

4'-methoxy-4-aminoazobenzene,

2-methyl-4'-methoxy-4-aminoazobenzene,

3> 6, ^ '- trimethoxy-4-aminoazobenzOl,

4'-chloro-4-aminoazobenzene,

2'- or 3 * -chloro-4-aminoazobenzene,

3-nitro-4-amino-2 ^! , 4'-dichlorazobenzene and 4-aminoazobenzene-4'-sulfonic acid amides

The group A is preferably the remainder of the formula

where c and d are hydrogen atoms, lower alkyl radicals, such as methyl, Ethyl, lower alkoxy radicals such as methoxy, ethoxy, and Are phenylthio or phenoxy radicals.

The group c is preferably bonded in the ortho position to the azo group and can in addition to those mentioned above Groups also a chlorine or bromine atom, a trifluoromethyl group, an alkylsulfonyl, preferably a methylsulfonyl group and one optionally alkylated on the nitrogen atom, preferably methylated acylamino group, in which the acyl radical is the radical of an organic Mpnocarboxylic acid, such as acetic, chloroacetic ,, Butyric, benzoic, pyridinecarboxylic or thiophenecarboxylic acid one organic monosulphonic acid, such as methane, ethane or p-toluene monosulphonic acid, or the residue of a carbamic acid or a carbonic acid monoester, such as Phenoxjrcarbonyl- ·

Methoxycarbonyl, butoxycarbonyl and a CONH _p group or the radical Z is.

The groups R ₁ and R _p can be hydrogen atoms

or lower, i.e. 1 to 4, preferably 2 to 4 carbon ■ alkyl groups containing atoms, such as methyl, ethyl, n-propyl

or n-Buty! groups which can be substituted in the usual way or interrupted by heteroatoms, especially oxygen atoms, such as benzyl, β-phenethyl, halogenated alkyl groups, such as β-chloroethyl, β, β, β -Trifluoroethyl, β, γ-dichloropropyl, ß-cyanoethyl, cyanoalkoxyalkyl, such as ß-cyanoethoxyethyl, alkoxy-alkyl, such as ß-ethoxyethyl, ^ -Methoxybutyl-, ^ -Butoxybutyl, hydroxyalkyl, such as β-hydroxyethyl, β, γ-dihydroxypropyl, nitroalkyl, such as β-nitroethyl, carbalkoxy, such as β-carbo (methoxy, ethoxy or propoxy) ethyl (the terminal alkyl group in 'ω-position can carry cyano, carbalkoxy, acyloxy and amino groups), ß- or Ύ-carbo (methoxy or athoxy) propyl, acylaminoalkyl, such as ß- (acetyl or pormyl) aminoethyl , Äcyloxyalkyl, such as ß-acetyloxyethyl-j ßjY-diacetoxypropyl, $ .- Propionyloxyethyl- ^ ß-butyryloxyäthyl-, ß- (alkyl or aryl) sulfonylalkyl, such as ß-methanesulfonylathy 1- ,. ß-Aethanesulfony-1 · ethyl- or $ - (p-Chlorben2olsuirbnyl) ^ ethyl-., Alkylearbamoyloxyalkyl-> v? ie ^ -Methyl-carbafflyloxyathylcarbamyloxyEthyl-, Äikyloxycarbonyloxyayioxyiät *, like $ ^ ' Ethyloxy- _s ^ piOpyl-i 0- {p- ^ itro | 3heiiöxy) "- ethyl ^, β - {p-Hydroxyphenoxy)« ethyl- »(ß- ^f (] ß ⁱ -Auefeyläthoxycarbonyl) -äthyl-> fi- t # * »cyano- _# - hydroxy-» methoxy- or ethoxy- ^ methoxycarboilyl-ethyl-, β

■ 0 09883/195 8

ß-Acetyläthy 1-, ß-Cyanacetoxyäthyl-, ß-Benzoyl- ,, ß- (p-Alkoxy- or phenoxy-benzoyl) -oxyethyl groups.

_{R 1} and / or R _{p are} particularly preferably denoted

a remainder of the formula

-Alkylene-NR ^ -Z

wherein Z is the same as above and R ₂ ^ is a hydrogen atom

or an alkyl syrup, preferably with a maximum of 4 carbon atoms, or an aralkyl group.

The groups R 1 and R p generally contain

no more than 18 carbon atoms.

As disazo dyes there may be mentioned, for example, those in which two identical or "different molecules of monoazo dyes of the general type of formula

D-N = N-A '

where D and A ^{1 have} the same meaning as above and A 'also' can be a radical of the formula -A-NR ₁ -Rp, connected to one another via their coupling components by a divalent bridge Z ¹ without dye character, where either the dye residues 'or the bridge Z' carry a residue of the formula -NR, .- z.

Styryl dyes.,

Preferred styryl dyes are those of the formula * '

009883/1933

NC

where A, R, and R _{p have} the same meaning as above and Y is a cyano, carbonamide, carbalkoxy or arylsulfonyl group, such as a carbethoxy or N-alkylcarbonamide, N-arylcarbonamide, N ^ N-dialkylcarbonamide, Phenylsulfonyl group, and where at least one of the radicals R ,, Rp or Y must contain the radical -NRj, -Z.

The dyes of the formulas are particularly preferred

NG NG

-CH ₀ CH ₀ -CH ₀ -MZ, C = GH <> ML R ₀

1 2 2 2 4 and _{qq /} ⁿ - 'α 2

' ^J NH-arylene-M Z

in which the radicals R, and Z have the same meaning as above,

Preferred bisstyryl dyes are those in which two moriostyryl dye molecules of the type *.

NC

C = CH-A-NR ₁ R ₀

which can be the same or different from one another, and in which Y, R ,, R "and A have the same meaning as above, are connected to one another via the radical A or the group R through a divalent bridge Z 'without dye character, where at least one the radicals R ,, R , A or Z ¹ carries a fiber-reactive radical Z.

009883/1958

Anthraquinone dyes.

Anthraquinone series dyes according to the invention are, for example, anthraquinone derivatives of the formula

η.

wherein η 2 or, preferably is 1, Z R.und the _same: meaning as above and A denotes an anthraquinone radical having 3 to 5 x fused rings containing one or more other substituents such as halogen atoms such as fluorine, chlorine or bromine Hydroxy groups, alkoxy groups, amino groups, acy / amino groups, alkyl / amino groups having 1 to 3 carbon atoms, acyloxy groups, such as arylsulfonyloxy, in particular p-toluenesulfonyloxy groups, optionally substituted aryl radicals _; optionally substituted heterocyclic radicals, arylamino groups, where the aryl radical is preferably a phenyl group which can be substituted by one or more halogen atoms, alkyl or alkoxy groups, alkyl or optionally substituted phenylsulfonyl groups, alkyl or optionally substituted phenylthioether radicals and nitro, cyano , Carboxylic acid ester and acetyl groups. Examples of tetracyclic anthraquinone residues are 1,9-isothiazole anthrone, 1,9-anthrapyrimidine or 1,9-pyrazole anthrone. The alkyl radicals are preferably lower alkyl radicals which can contain up to β carbon atoms.

009883/1958 *

The new dyes are prepared a) by reacting a dye which contains at least one group of the formula -NHK, in which R has the same meaning as above, with at least one fluorinated s-triazine of the formula Z- ^ F, or b) by linking 2 components, of which at least one component contains at least one group Z bonded to an amino group, by condensation or coupling to form the eleventh dye which contains at least one group Z, where Z in each case has the same meaning as above Has. . . '/ I. Process variant a) A. Fiber-reactive acylating agents.

As a fiber-reactive acylating agent, which the

Introduce radical Z, fluorinated nitrogen-containing heterocycles are used, but preferably triazines, such as trifluorotriazine, difluorochlorotriazine or a mixture of the two.

The difluorotriazines, which are still an Al- are obtained. contain kyl, aryl, amino, alkoxy, aryloxy or thioether groups most conveniently from the corresponding Dichlortr.iazine.n, those with a fluoride, such as potassium hydrogen fluoride, with or without a solvent, such as sulfolane ^. Nltrobenzol and the like in

Converted to fluorine derivatives; will.

Suitable difluorotriazines are e.g. 2-ethyl-4,6-

difluor-triazine, 2-ethoxy-4,6-difluorotriazine _/ 2-phenyl-4,6-difluorotriazine, and 2-ethylmercapto-4,6-difluorotriazine.

B. Dye components: '

As the reactive components, there are, for example, the following Suitable dyes:.

009883/1958

l) azo dyes.

OH

-N = N- ^ O-NH ₂ , H-C0-d> -N = N-

NH,

-N = I

GN

/ ° 2 ^Η 5 JN

CH.

NO

H ₂ N-

-N = N-C C C-CH

HO-C N

H ₃ C

-N = N-

-C — CIL II '

-ΝΗ _Λ

HC N

O ₂ NC CN = N

Cl OH

N = N-C = C

> ΚΙ> ΝΗ

Cl ^X

CH

009883/1958

g) Anthraquinone dyes ^

1,4-diaminoanthraquinone, '.

l-amino-4-hydroxyanthraquinone,. - '·

1,4-Bis- (p-amino-anilino) -5 ~ hydroxyanthraquinone.,. ·

l _i 4-bis- (p-amino-anilino) -5i8-dihydroxyanthraquinone, l, 4-bis- (p-amino-anilino) -2-niethylanthra-ghinone, l _i 5-bis- (p-amino-anilino) - 4 _i 8-dihydroxyanthraquinone, - ■

l-Hydroxy- ² l - (p-amino-anilino) -anthraquinones · ·. ■ 5-Amino-1,9-i ^s ° thiazolanthrone _i "· '.'; · ■" - '· 4-amino -l _/ 9-anthrapyrimidine, ·:. ' ■ "'. ·; · '"".,' - · · 5-Amino-l, 9- ^a nthrapyrimidine, '. ■ '

2- or 3-aminobenzanthronj ·. · ''. i

5- or e-Amino-lj ^ -pyrazolanthron / '. ·' '. ·. "·.

NO

NO ₂ .

009883/1958.

- "" "" "" "3JAIa,

C- <O-NH- <> - SO ₂ -CH ₂

no.

4) styryl dyes:

2 * 5

-N-GH _n CH,

N (C ₂ H ₄ OOCGH ₃ ) ₂

GH.

NH- <V-NH,

5) quinophthalone dyes :

6) pyridone dyes;

GH.

009883/1958

.7) Perinon dyes:.

The mixtures of the dyes of the formula

or, the mixtures, of the dyes of the formula

X X

wherein in each case one X stands for a group of the formula -NH _p and. an X stands for a hydrogen atom.

C. Implementation Conditions. _i . · ■

The reaction with the acylating agents is usually carried out by adding the acid halides to the acylating amines, mostly in organic solvents such as methylene chloride. Chloroform, carbon tetrachloride, Benzene, chlorinated benzenes, chlorinated higher aromatic hydrocarbons, diisopropyl ether, Dioxane, acetonitrile, glacial acetic acid and 80% acetic acid, or

? » / toco

a / in acidic aqueous solution or with / suspension of the to

acylating dye works.
II. Process variant b)

A. Azo dyes (coupling).

The azo dyes according to the invention can e.g. by coupling a diazonium compound of an amine with a Coupling component are obtained, at least one of the components, preferably the coupling component, a fiber " reactive group Z must contain.

The above-mentioned diazo components of the formula D-NIL can be used as diazo components without a fiber-reactive group Z be used.

Suitable coupling components which contain a fiber-reactive group Z are obtained by reacting one of the The following components are obtained with an acid halide of the formula Z-HaI:

3-Amino-N, N-bis-ß, ß-acetoxyethyl-aniline, ^ -amino-1 ^ N-bis-ß ^ -cyanoethyl-aniline, j5-amino-N, N-bis-methyl-aniline,
Ν, Ύ-ainopropyl-N-ethyl-aniline,
jS-Amino-NjN-bis-ethyl-aniline,

009883/1958

The diazotization of the diazo component mentioned! can be done according to methods known per se, e.g. with the help of Mineral acid and sodium nitrite or e.g. with a solution of nitrosylsulfuric acid in concentrated sulfuric acid, take place. ',

The coupling can also in a known manner, for example in a neutral to acidic medium ^1, optionally in the presence of sodium acetate or the like, the influence Kupplüngsgeschwindigkeit buffer substances or catalysts such as dimethylformamide, pyridine, resp. its salts, are made. ·

The coupling takes place with advantage also under Combination of the components in a mixing nozzle. This is to be understood as a device in which the to Mixing Liquids "on relatively small Spaces are united with one another, with at least the a liquid, preferably under increased pressure, is passed through a nozzle. The mixing nozzle can, for example be constructed according to the principle of the water jet pump

and work, the supply of one liquid · . 009883/1958

EAD ORiGiWAL

in the mixing nozzle of the water supply, in the water jet pump and the supply of the other liquid in the mixing nozzle the connection in the vessel to be evacuated corresponds to the water jet pump, this latter supplying liquid can also take place under increased pressure. For rapid, possibly continuous mixing However, other suitable devices can also be used in a small space. . '.

III. Use.

The new water-insoluble dyes, their mixtures with one another and their mixtures with other azo dyes are excellent for dyeing and

'Baumwo 12_e. ^ __ regenerated cellulose, / printing on leather,' wool, silk, and above all ~~

synthetic fibers, such as acrylic or acrylonitrile fibers, polyacrylonitrile fibers and copolymers of acrylonitrile and other vinyl compounds, such as acrylic esters, acrylamides, vinyl pyridine, vinyl chloride or vinylidene chloride, copolymers of dicyanoethylene and vinyl acetate, as well as acrylonitrile block copolymers, basic modified polyolefin fibers, fibers made of polyurethane such as polypropylene, and Cellulosetrl- _i 2 1/2 acetate, and particularly fibers made of polyamides such as nylon-6, nylon-6,6 or nylon 12, and aromatic polyesters such as * from terephthalic acid and ethylene glycol or 1,4-dimethylcyclohexane , and copolymers of terephthalic and isophthalic acid and ethylene glycol.

009883 / 19B8

BATH ORIGINAL

For dyeing in aqueous fluids. Using the water-insoluble dyes zweckmll -, & ig in finely divided form, and color with the addition of dispersing agents such SuIfitcelluloseablauge or synthetic detergent, or a combination of wetting and dispersing agents. As a rule, it is expedient to convert the dyes to be used into a dye preparation which contains a dispersant and finely divided dye in such a form that when the dye preparations are diluted with water, a fine dispersion is formed before dyeing. Such dye preparations can be obtained in a known manner, for example by grinding the dye in dry or wet form with or without the addition of di-porous agents during the grinding process.

The new dyes dye hydroxyl-, amino- ι-ί · Ί / or fibers containing amide groups, especially polyamide fibers, from weakly alkaline, neutral or weakly acidic baths, e.g. from acetic acid baths. As a special advantage of the new Dyes should be mentioned that they contain nylon fibers in a very broad range, from acidic to alkaline values, satisfactory to dye. This also applies to wool.

The dyeings and prints obtained on polyamide fibers and wool with these dyes are excellent Wet fastness properties, especially good light, wash, sweat B-j, Walk and water fastness.

To achieve strong dyeings on polyethylene terephthalate fibers if it proves to be expedient to

009 883/185 8 bath original.

bath to add a swelling agent, or else ^{to carry out the dyeing process under pressure at temperatures above 100 °} C., for example at 120 ° C. Suitable swelling agents are aromatic carboxylic acids, for example salicylic acid, phenols, such as, for example, o- or p-oxydiphenyl, aromatic halogen compounds, such as o-dichlorobenzene or diphenyl.

This is used to heat-set the dye padded polyester fabric, appropriate after previous

Drying, e.g. in a warm air stream, to temperatures of over 100 C, for example between 180 and 210 ° C.

The dyeings obtained according to the present process can be subjected to an after-treatment. for example by heating with an aqueous. Solution of an ion-free detergent.

Instead of by impregnation, the specified dyes can also be used according to the present process can be applied by printing. For this purpose, one uses, for example, a printing ink that, in addition to those in the Aids commonly used in printing, such as mesh and thickening » medium, which contains finely dispersed dye »

. The present process would give strong dyeings and prints with good fastness properties ₀

009883/1958 _ _1NA ,

BAD OBIGtNAL

Organic liquors can also be used instead of aqueous dye liquors. For exhaust dyeing, liquors made from chlorinated aliphatic hydrocarbons, such as tri- or tetrachlorethylene, which may contain solubilizers such as dimethylformamide, can be used. Mixtures of chlorinated aliphatic hydrocarbons and solubilizers can also be used for padding. There are also emulsions which, for example, contain 1 - IC. "V / water and 90-99 $ tetrachlorethylene.

You can use the new water-insoluble dyes also use for spin dyeing of polyamides, polyesters and polyolefins. The polymer to be colored is expediently in the form of powder, grains or chips, as a finished spinning solution or mixed with the dye in the molten state, which in the dry state or is introduced in the form of a dispersion or solution in an optionally volatile solvent. To homogeneous distribution of the dye in the solution or melt of the polymer is the mixture in a known manner by casting, pressing or extruding into fibers,

009 883/19 5 8 bad original

Yarns, monofilaments, films etc. are prepared.

In the following examples, the parts mean, unless otherwise stated, parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

009883/1958

Regulation I. N-bis-ß-cyanoethyl-3- (cc'β '-dibromopropiony]) -amino-aniline,

5j3 parts of N-bis-ß-eyanethyl-3-amino-aniline are dissolved in acetone ₃ reacted with a small excess of difluorochlorotriazine and stirred for some time. A product of the formula is obtained

Regulation II .

N-bis-ß-acetoxyethyl-3- (α *, β'-dibromopropionyl) -amino-ahiline.

14 parts of N-bis-acetoxyethyl-3-amino-aniline are dissolved in acetone. A small excess of trifluorotriazine is added and the solution is stirred for some time. After Determination of the coupling titer can be the product of the formula

C_H.-OC-GH " ^{2 4 5}

Nj_h. -oc-ch ⁴ 11 -

• T ° NC. .

NH-C if

can be used without further purification. In an analogous way, the following

00il83 / 1iS8

Coupling components manufactured:

Regulation III,

9.7 parts of N-ß-oxyethyl-N-7-aminopropyl aniline been dissolved in acetone. You give a small allowance Add trifluorotriazine and stir the solution for some time. To the determination of the coupling titer can be determined by the product of the formula

V Λ

\ LEL -— HH G N

3 6

can be used without further purification. The following coupling components are produced in a similar manner:

G _O H _{C w} GH

^{2 5} CH, f C> N ^{/ 2 5} CH

⁵ - H -N /

2 ^H 4 V

009883/1951 '

. -27-

Regulations IV.

24.8 parts of ß-nitro-isophthalic acid chloride will be dissolved in chlorobenzene. A solution of 35.8 parts is added dropwise. N-ethyl-N-oxyethyl-m-toluidine in chlorobenzene and then stir the mixture for some time at 100. The hot solution is then diluted with sodium hydroxide carried out. The precipitate is stirred for a short time, then the chlorobenzene is removed by steam distillation. The aqueous phase is separated while the "sticky Product is taken up in chloroform. The remaining water is separated off and the chloroform is distilled off. You get the product of the formula

CH, '. . CH, ■. '· ■■ ·.

^H 5%.

10.6 parts of the product obtained above werderr suspended in ethyl alcohol and hydrogenated with the addition of palladium carbon as a catalyst. The alcohol is then distilled off and the oil is left in the room for a longer period of time.

left to stand at temperature, whereupon it crystallizes. Man . receives a product of the formula

., ".. 00988-3" / 1958

'....' ·· '". ·. · - ■ - · ... · ^ß AD ORIGINAL

11.9 parts of the amine obtained above are dissolved in acetone at room temperature. A small amount is then added Excess trifluorotriazine and stir overnight at room temperature. After determining the coupling titer, the product of the formula.

M C 1

K = G

can be used without further cleaning,

Regulation V. '

Ιβϊ parts of p-nitro-benzoyl chloride (95 l # ig) is suspended in chlorobenzene and heated to 80 "by dripping a solution of lhj _ß h- parts of N-ethyl-N-m-toluidine in ßhydroxyäthyl-chlorobenzene. The mixture is then stirred for some time, then the reaction mixture is poured onto dilute sodium hydroxide solution, a few tenths are stirred, the initially strongly alkaline solution becoming acidic The residue is allowed to cool, the product crystallizing out. After filtering off, the residue is washed well with water and dried. The product obtained is suspended in ethanol and hydrogenated with the addition of palladium-carbon as a catalyst . the suspension is heated to boiling, filtered hot and the filtrate is concentrated. The precipitated product is filtered off and washed with ethanol. After drying in vacuo, a product of the formula is obtained. ■. ■ ·. '· ..... "

^ IMSPSCfEO

-H

14.9 parts of this product are dissolved in acetone. To this are added a slight excess Trif 1 "Ortriazin ^ and the solution is stirred _o some time gives a product of, formula

N = G \ F

After determining the coupling titer, the product can be used directly

be used,,
"Similarly, the coupling component

the formula

O ₀ IL-CM

c _o Ho- ~ eo ~ <I> -iH - c ι

E = Q

manufactured

009883/1351

•Example 1. *

J ₃ I parts of 2-cyano-4-chloro-aniline are introduced into 20 parts by volume of 2N hydrochloric acid. At a temperature of 0 to 5 ° C., the mixture is diazotized with 4N sodium nitrite solution and stirred for some time. The excess nitrite is then mixed with urea destroyed".

This solution is added dropwise at a temperature of at most 10 ° to a solution of 7.9 parts of N-bis-β-acetoxyethyl-3- (difluorotriazinyl) -amino-aniline in 125 parts of acetone, stirred overnight at 0 to 10 ° and the dye is precipitated by addition from ice water. After filtering, the dye is washed neutral and dried in vacuo. You get one Dye of the formula

PN

C ₉ HO-CO-GH _x

NH- - C N

\ / N = C

which dyes nylon fibers in yellowish red shades of excellent wash fastness »

Example 2.

If, instead of the above-mentioned N-bis-ßacetoxyethyl-3- (difluorotriazinyl) -amino-aniline, 6.6 parts of N-Bs-ß-cyanoethyl-3- (difluorotriazinyl) -amino-aniline are used, a dye of the formula is obtained

009883/1968 '

Cl-

-N = N

N = C

N-C

which dyes wool fibers in orange-red tones »

If the diazo compounds of the amines mentioned in column I are coupled with the coupling component indicated in column II under the conditions indicated in example 1 * this is how reactive disperse dyes * the polyamide fibers are obtained color in the shade indicated in column III, if none other fiber type is specified »

009883/1958

No. ₀ I. II y 0
γλ TJ July c \ c * r * n < 0
ir
C _o H.-0-0-CH "
_p 0 _A -OC «H ₃ 0 ■
Il C ₀ H ₁ -OC-CH, III * 1 2-amino-6-
ethoxy-benz-
thiazole I. P 0
}
NC
/ A ^
iIPC N
\ /
H = C j KJ
NC C _O H.-CC-CH_
s W 2 4 3 Il
P 0
I. reddish
violet P. NH-C N
N = C
Γ
P. NC
ec ν • N = C 2
■ 2-amino-5-nitro-
thiazole 1 "blue I.
P. 3 4-nitro-aniline Red

009863/1958

- 54 -

No.

4 '■ 2-cyano-4-nitro-! aniline

2-trifluoroethyl-4-chloro-aniline

-N

Ng / II

NH-C N N / N = G

N-C

IH-G I N /

N-C

III

I purple

Red

C.H.-O-C-GH » 2 4

H-O

IH-G I

Red

Ö0S883 / 19S®

No. "ι

7;

II

G-NH,

Cl

H.

III

violet

C_H.-0-C-CH
4th

Red

009883/1958

Orange red

T ~

No.'

10

'

:

i

14th

O N-

CN

■ MH,

Cl

-NH,

Cl

-NH, II

N-G

HN-C

"N

N = C

NH-C
\

N = C

I τ

III

violet (on polyester)

Red

Red

Red

reddish purple

No. II

III -

15 16

17 Cl- <_> -IIIH, CP, -G 'H -CN • Ν / ²

NH-C
\

N-C

N = C

<Γ

σ_Η, - (

_ _Ν / 2 4 j

C ₂ HO-COCH

NH-C
\

N-C

N = C F

NH-C
\

N-G

C ₀ H ₇₁ -O-COCH ² 4

N = G F

009883/1958

orange yellow

orange

Red orange

No,

18 ι Cl-

; 19th

! 20th

-NH,

COOGH

COOCH

Cl

CILO ₀ S-3

• NH. II

N = C

III

orange

G HO-COCH, _T / d

NH-C
\

N-G

C ₂ HO-COCH

N = G

I P

Orange red

golden yellow

Orange red

P 'H · S

I-G

003883/181

No.!

22 I.

Cl

CN

23 O,

Cl

: 24

CH ₃ O ₂ S

-NH,

OCH.

26th

OCH, II

C_H.CN

^4th

III

C H -O-CO- <I3> -N /

CJS.-OH

^4th

O_H _C -NH-C N

6 \ /

01

C ₀ H ₁ -OH
ON / ^{2 4} H

N = C

N-C

F.
Cl

N = C

/ N

* V /

N-C

l

₄ -CN

Cl

NH-C
\

N-Q

N = C

orange F

N = C

violet

orange

orange

Scarlet fever

009883/19 R «

; nc OCIL

OCH.

-NH,

C _o H _r
/ 25

C ₀ H -0-CO-CH
/ 2 4

-Cl (-o)

-NH,

NH-C
\

N-C

N = C

JCH ₃ -0-C (

Cl

30; 0 _o N- <> -NH _o

\ _N AA _S /

C-NH,

CH-CO III

Scarlet fever

H
-N ⁷ NC

\ N

N = C /

bluish tint

Red

(on polyester)

red (on PoIy-TT Pester)

/ I

. C N

P F

U-α blue-

-N ^ Nn stinging

NJ H -OC <KI> NH-C N _red

/ 24

NH-C N-C

purple (on nylon)

00988b / 1958

No. I.

32 ^:

UO ₀

NI

34 H ₀ NO ₀ S--

HiL

■ cii

ί 35 ^: CL-d> NIL

- 41 -

ir

III

O ₀ H ₁ -OH

-Ή

UH-O \

N-G

H = O

-IY

C ₀ HO-OO-OIU 2 4 J

N-C

NH-ß

H-O

-N.

₀ H

Cl

N = C / \ -00 N ^ // ' NC

'' yellow-orange

Orange red

yellow-orange

'^ 3 ϊ yellowish tinge Red

BATH ORIGINAL

.0 0 ^l ) 0 B 3 / I 9 ζ

No, !

36: Cl-

37

, i CHjC

(Ji

NILE

GL

4-NLtro-aniLin

II

C ₀ H-GN

²

N-G

HH-G ^; \

N-G

Eq

G ₀ H -0-CO-CH- / 24

N = G // \ NH-G II

N-G

III

Orange red

orange

yellowish red

CH ₀ -CH-GO-CH ²

NC // ^, NH-C N \ /

N = C

009883/1358

Red

ORIGINAL INSPECTED

No.

2-chloro-4-nitroaniXine

41

- 42

• 43

2-cyano-4-chloro aniline

2-chloro-4-nitroaniline

2-chloro-4-methylsulfonyl-aniline III

: bluish red

• yellowish red

D0 9883 / 19E8

No.

44 ■ 2-chloro-4-methylsulfonyl aniline

j 45, 2-cyano-4-chloro! aniline

II

III

CH-CH-OCOC ₀ H 22

^oran S ^e

CH / 2

-N

25 (on wool)

2 * 2 P

N-C

NH-C N

N = C

-N \

NH-CO-NH-C ₀ H _n

O":

C ₀ H, - / ²⁵ O

NH-SO ₂ CH ₅

09883/1958

yellowish

-NH-C N

N = C

NC //

N = C

No,

48 ■ 4-mitro-aniline

49 2-cyano-4-nitroaniline

50 2-cyano-4-chlorine, anILine

2-Oyan-4-chloroaniline

II

III-

Red

GH

violet

CH-CH-GH ₉ -OG-CIL.

NH-C N

■

Il

^ CH ₂ -CH ₂ -OC-CH ₂ -CH ₂ -CH ₃ ge Lb- -h 'pithy

Red

CH-GH-O-C-GH-CH-CH.

NO
// ^ NII-C 'N \ /

009881/195

yellowish red

No,

52

2-chloro-4-nifcroariiline

2-Trifluoromebhy L-4-chloro-ani-LLn

54,2,5-dimethoxy-4-cyaii-anilLn

j 55 ■ '2-chloro-4-methyl-, ijuLfonyl-aniline

II

0 ₉ Η _Γ / 25

NH-G N

N = G

I ρ

GI

P ^ά

N-G

NH-G N

N = G

/ Α " ⁰¹

ir - σ

NH-G N

N = G

III

P *

NC // ^ NIFC N \ / - ■

N = G

bluish \ red

orangero b

009883

Red orange

1953

No. _β

II

56; 4-aminosulfonyl-1 aniline

57; 2-cyano-4-chloroaniline

2-Ohior-4-methylsulfonyl-aniline

-N
\

NC // ^

NH-C N

N = C

III

yellow-orange

orange

orange

009883/1958

No. I. It II F.
C.
N
/
C.
\
F. III 59 ' 3-amino-5-nitro-
benzisothiazole It 3
N -
C.
\
N = blue
(on poly
ester) 60 3-amino-5-nitro-
7-bromo-benziso
thiazole Il Il 61 3-amino-benziso
thiazole It blue
violet 62 3-amino-5-chloro
benzisothiazole "1 ti 63 3-amino-7-chloro
benzisothiazole H It 64 3-amino-4-chloro
benzisothiazole It - Il \ 65 3-amino-5,7-di-
.brombenziso-
thia.zol Il ; 66 3-amino-5-chloro
7-bromo-benziso
thiazole It

009883 / 19S8

Example 3 » '

4 parts of 1-hydroxy-4- (p-aminophenyl) -amino-anthraquinone v / earth suspended in 50 parts by volume of glacial acetic acid. In addition a small excess of trifluorotriazine is added and the suspension is stirred for some time. Then you wear the mixture on ice water, filtered off and washed the Residue well with water. After drying in vacuo, a dye of the formula is obtained

0 OH

N = C
0 NH- <r ~> -liH-C N

N-C

\
F.

which dyes nylon fibers in blue tones.

In an analogous way, starting from the corresponding Aminoanthraquinones obtained the following:

009883/1958

0 OGIL

Yellow shade on polyamide

orange red

golden yellow

Scarlet fever

blue

0098) 93/1958

0 NH ₀ P. -C ₂ H ₄ -OH F.
■ F. j Nu «nce ^on polyamide I. ( blue O ] | J
-C ₂ H ₄ -OH ^ nC ^ I. * Il (Y) N-C > r- _s NC j blue CC k / V ¹
Il ü I. NCJH-C N blue Il O Y - <> -NH-C N . F. \ / Il \ / F.
■ N = C O NH- N-C I. I. I // ^, F. F. NH-C N Cl
I. \ / I.
NC O N = C <> - NH-C N O
ti Il NH- ^A f \ / co Λ I.
NC N = C blue Y? 0 ν I. HN
I. 0 NH- NH- <> -NH-C N F. 09883/1 S 5 8 Cu OH P. W.
Il 0 ν HH- 0 Cf] k / U
η Il
0 KH ₂ blue - I. NH ₂ blue γ NH- OH
ι NH-

~ ⁵² "

example

To a suspension of 3.9 parts of 4'-thiopherioxy-1,2-naphthoylon-'l-amlno-bonz; imlda / iol in 80 parts of glacial acetic acid there is a slight excess at room temperature Trifluorotriazine added dropwise; the mixture is stirred overnight and the dye is precipitated by adding ice water. After filtering, the dye is washed neutral and dried in vacuo. A dye is obtained the formula

which dyes polyamide and polyester fibers in golden yellow tones with good all-round fastness properties.

009883/195 8

BATH ORIGINAL

Example 5 « '

11.4 parts of 4-amino-naphthoylene-benzimidazole are suspended in 160 parts of glacial acetic acid. A small excess of trifluorotriazine is added dropwise at 25 ° C. and the mixture is heated to 40-45.degree and stir overnight, the dye is precipitated by adding ice water, filtered, washed neutral and dried in vacuo. Man receives a dye of the formula N.

M: C G-F

Ii ^: N

of the polyamide and polyester fibers in greenish yellow shades colors.

009883/1958

Example 6.

2.3 parts of 3-chloro-4-aminophenylmethylsulfone ($ 90.5) are at 20 to 25 ° with 100 parts by volume of 0.5N-nitrosylsulfuric acid diazotized, stirred for one hour and diluted with 20 parts by volume of a mixture of glacial acetic acid / propionic acid (6: 1). This diazo solution is at 0 up to 5 to a solution of 3 * 1 parts of the amine (regulation IV) added dropwise to 100 parts by volume of acetone. The coupling has ended after 3 hours. The dye of the

is precipitated by adding sodium acetate solution, filtered off with suction, Washed neutral and dried ". An orange-red product is obtained, which consists of nylon fibers in red tones colors.

009883/1958

Example 7.

Parts of the product of the formula

CJEL

are in acetonitrile with a catalyst of 10 $ palladium hydrogenated on charcoal until the amount of hydrogen required to reduce the nitro group has been absorbed. In the thin-sight chromatogram the starting material is no longer visible. The acetonitrile is distilled off and the residue in glacial acetic acid implemented with a small excess of trifluorotriazine. The dye of the formula is obtained

C = CH- <~> -N
1-

N 1
NC · "C _o H-O-CO- <r> -NH-C CF

■ 3  ⁴

which dyes nylon fibers in greenish yellow tones.

009883/1358

-56, - . . ■ '203-326

The same dye is also obtained by acylating the product of the formula

■ · CN / ^G 2 ^H 5

CN '~ 2 "4

with the acid chloride of the formula |

■ NG // \

Cl-CO- < > -NH: C N

\ / N = C

This acid chloride was obtained by acylation of p-aminobenzoic acid with trifluorotriazine and subsequent reaction with thionyl chloride obtain.

The following dyes are obtained in an analogous manner and dye all polyamides in greenish yellow tones.

009883/1958

C = CH-

Λ ^Η 5

-N

CH,

N-C

N = C

C = CH-

CH

N-C

-NH-C

N = C

\ _P

C = CH

C = GH

CONH

N = C

CONH-

/ ° 2 ^H 5

NC // ^ -CN

N = C 009883/1958

20332B3

O = CH-

COHII-

C ₀ II ₁ -OCIL / 24

-N

-ITH

H ₄ -OCH HC

C H

N = C
Np

C = Ci

C,

O ₂ H ₄ -OO-

N-C-NH-C N

N = C

CH.

CONH-

NH-N-G

N = GN _P

009883/1358

C = CH-CONH-

-N

-NH-

N-C

N = C

009883/195 8

-6ο -

Example 8.

By condensation of p-nitroaniline with cyanoacetic acid in toluene with azeotropic removal of the water formed, the derivative of the formula is obtained

CN CH COlffl-

4.3 parts of this product are in 50 parts by volume of methanol and 5 drops of piperidine with 5.9 parts of N, N-di-ß-acetoxyethylp-aminobenzaldehyde condensed. The product of the formula is obtained in good yield

-N (C ₂ H ₄ OCOCH ₅ ) ₂

By catalytic reduction with Raney nickel in dimethylformamide until the amount of hydrogen required to reduce the nitro group is absorbed, the product of the formula is obtained therefrom

N (C ₂ H ₄ OCOCH ₃ ) ₂

2.25 parts of this product are mixed with a small excess of trifluorotriazine in 20 parts by volume of glacial acetic acid at 15-20 ° and the mixture is stirred at 15-20 ° for 20 hours. The dye of the formula

009883/1958

is filtered off with suction, washed with methanol, dried. He colors Polyamide fibers in vivid greenish yellow toners. In an analogous manner, reaction with difluorochlorotriazine is obtained the dye of the formula

.CN

N) = CH-CONH- <~~> -NH-

N-C -C N

which dyes polyamide fibers in greenish yellow tones,

008883/1953

Example 9

19 * 55 parts of ^ -amino - ^ - chlorobenzotrifluoride will be diazotized in the usual way and with 19 parts of 1- (3'-Am ± nophenyl) -3-methyl-5-pyrazolone coupled. The new monoaza dye is isolated and dried.

19.77 parts of the dye are stirred in 200 parts of toluene and, at 60, a slight excess of trifluorotriazine in 20 parts of toluene is added dropwise over the course of 20 minutes. The mixture is then heated to 60 and stirred for 6 hours. After cooling, the ¹ becomes new dye of the formula

Cl OH As.

UH C C-P

I = NC = C _x

I I

CH ₃ F

isolated, washed with petroleum ether and dried. It is a yellow powder, the polyamide fibers in beautiful yellow Dyes shades with very good fastness properties.

A dye with the same good properties is obtained if the l- (4 ^l -aminophenyl) ~ 3-methyl-5-pyrazOloii is used as the coupling component »

008883/1318

The following dyes, which dye polyamide fibers in yellow tones, were prepared in an analogous manner and the formula -p

C-N

G-NH

N = N-G

G = N

where G is a residue of the formulas

OH

GH. OH

Eq

OH

009883/1958

OH

OH

A C- 0 -CH

and the dyes of the formulas

is,

OH

CHO-

-N = N-

N -

HN-C N

OH

C ₂ H ₅ -O-

-N = Jf-

N -

HN-C N

N =

0098 83/195 8

NO,

8 GH,

.Γ

N -

6 '

HG = N ύ-ö 'N

N =

I P

009883/1958

Example 10.

~ 5 ~ 5.6 parts of V-amino - ^ - nitro-diphenylamineT-l-sulfonic acid-N-ethylamide are dissolved in glacial acetic acid and stirred with a small excess of trifluorotriazine until the reaction has ended. The dye is then precipitated by adding water, isolated and dried in vacuo.

The sparingly soluble in water, in organic Lo- I

solvents but soluble dye of the formula

F. ~> -NH- 1- \ C-N // ^, _ N C-NH- <I \ / ^ - G = N
/ P.

is a yellow powder that dyes polyamide fibers in yellow tones with very good wet fastness properties.

009883 / 19S8

Example 11.

20.55 parts of ^ -amino-jS-chlorophenyl-methylsulfone are diazotized and coupled at 0-5 with 37 * 3 parts of 1- (difluorotriazinyl _T ) amino-7-oxynaphthalene in a weakly alkaline medium to form the monoazo dye.

The one insoluble in water, in organic solvents but soluble dye of the formula

is isolated and dried in vacuo. He represents a dark Powder that dyes polyamide and wool fibers in bright scarlet shades with particularly good wet fastness properties.

009883/1958

Example 12.

5.9 parts of 5-amino-1,9-pyrazolanthrone are in Suspended chlorobenzene. A small excess of trifluorotriazine is added dropwise at room temperature and then heated to 80 ° and stir for a while. Then it is allowed to cool, filtered the product off and washed with cold chlorobenzene. After drying in vacuo, a dye is obtained which Polyamide dyes in yellow tones.

Example 13.

Go with 10 parts nylon 6,6 tricot fabric ("Helanca") at 30 ° in a dyebath that is divided into 400 parts by volume Water, 8 parts of sodium bicarbonate and 2 parts of a 5% aqueous dispersion of that obtained in Example 1 Contains dye and has a p "value of 7.9. It is heated to boiling temperature in the course of 5 minutes and then dyed at the boil for 75 minutes. On that the textile material is rinsed well with water and dried. A brilliant yellowish red coloration is obtained with a high proportion of non-extractable dye. ·

009883/1958

Example l4.

The procedure is as in Example 13 , but instead of the sodium bicarbonate, 0.8 part of an adduct of 9 moles of ethylene oxide and 1 mole of nonylphenol is used, the

ρ value of the dyebath is 7 * 0. You get a similar one η

brilliant coloration as in Example 13 · - _,; ■

Example 15 »

The procedure is as in Example 13, but used instead of the sodium carbonate, 0.4 part of ammonium acetate and after 75 minutes, 0.1 part of 80% acetic acid is added. The p n value of the dye bath after the addition of acetic acid is 5j6. The textile material used is 10 parts nylon 6 tricot fabric ("Perlon"). A similarly brilliant coloration as in Example 13 is obtained.

009883/1958

Example l6.

'■' ■■ '. ·> · · The procedure * jie Jn Example 12, but used as a textile material 10 parts of bleached wool tricot fabrics »This gives a brilliant dyeing similarly as in Example 13.

If you then boil the tissue with an alkaline soap solution or a soda solution, you get special real colorations.

Example 17.

In a dyebath which contains 0® in 400 parts of water, 8 parts of an adduct of 9 moles of ethylene oxide and 1 mole of nonylphenol and 2 parts of a 5 # strength dispersion of the dye described in Example 1, one begins at J> 0 in a high-temperature dyeing machine Dyeing on 10 parts of polyester tricot fabric (textured polyester fabric "Crimplene"). The p "value of the fleet is 7.0. The temperature is increased to 120 ° in 15 minutes, a pressure of about 2 atil being created. It will be 45 minutes Oo

colored at 12 [beta] and then within 10 minutes cooled to 65 °. The textile material is then rinsed and cold

dried. You get a brilliant boil-proof and washable, but extractable orange coloring,

009883/1958

Example l8 .

It is colored as in Example 19., but used High bulk polyacrylonitrile tricot fabric (high bulk "Orlon" tricot). A brilliant, boil-proof and washable, but extractable orange coloration is obtained.

The dye dispersions used above are obtained by grinding 20 parts of dye with 140 parts of water and 40 parts of sodium dinaphthylmethanedisulfonate will.

Example 19 «

Go with 10 parts nylon 6,6 tricot fabric ("Helanca") at 30 ° in a dyebath that is divided into 400 parts by volume Water 0.2 part of 80% acetic acid and 2 parts of a 5% aqueous dispensing of the according to Example 1 Contains dye obtained and a p "value of 4-5

having. In the course of 45 minutes it is boiling heated and then colored at the boil for 30 minutes. Afterward is adjusted to a p "value of 12 by adding soda

ti

and cooked for another 30 minutes. Then the textile material rinsed well with water and dried. A brilliant yellowish red coloring with a high proportion is obtained of non-extractable dye.

009883/1958

Example 20.

It is mixed with 10 parts Ny1on-6> 6-tricot fabric ( "Helanca") at 30 ° in a dyebath which VoI. parts in 400 parts water 0.2 Qofaige acetic acid and 2 parts of a * 5 $ aqueous Contains dispersion of the dye obtained according to Example 1 and a p "value of

4-5. In the course of 60 minutes, the mixture is heated to 70 ° C., kept at this temperature for 15 minutes, brought to the boil within 30 minutes and colored at the boil for 60 minutes. The textile material is then rinsed well with water and dried. A brilliant yellowish red coloration with a high proportion of non-extractable dye is obtained.

009883/1958

Claims (1)

- ■ 73 - Patent claims. 1. Dyes free from water-solubilizing groups, characterized in that they contain at least one bonded to an amino group, a fiber-reactive radical Z of a nitrogen-containing radical substituted by at least one fluorine atom He.terocyclus included. 2, dyestuff according to claim 1, characterized in that that the group Z stands for the radical of an s-triazine which is substituted by at least one fluorine atom. J. Dyes according to claim 2, characterized in that that the group Z is a radical of the formula -G
ι I.
N N N
// S Y ^N V /
C. Vx N of which one K is a fluorine atom and the other X is an organic one Radical, in particular a hydrocarbon radical or a halogen atom is. 009883/1958 4. Dyestuff according to claim 3, characterized in that that one X is a fluorine atom and the other X is a fluorine atom, a chlorine atom, a substituted amino group an alkoxy group, a hydrocarbon group or an alkyl mercapto group is. 5. Dyestuff according to claim 4, characterized in that that both X are fluorine atoms. 6. Compounds according to claims 1 to 5, characterized in that they are azo dyes. 7. Compounds according to claim 6, characterized in that that they are monoazo dyes. 8. Compounds according to claim 6, characterized in that they are disazo dyes. 9. Compounds according to claims 1 to 5 * thereby indicated that they are anthraehinoid dyes. 10. Compounds according to claims i to 5 * 009883/1958 characterized in that they are styryl dyes. 11. Compounds according to claims 1 to 5j characterized in that they contain perinones, quinophthalones, Are pyridone dyes or nitro dyes. 12. '' Monoazo compounds according to claim 7j. characterized by the formula where D is the residue of a diazo component, A. is an arylene residue, in particular one in the m-position to the azo group is preferred unsubstituted 1, ^ - phenylene radical, R, and Rp each an alkyl " ···. '' are a group where- in at least one of the radicals D, A, R. and Rp one to one Amino group-bonded fiber-reactive radical Z contains. 15. Compounds according to claim 12, characterized in that that the group A is in the ortho position to the azo group carries a group of the formula -NR ^ -Z in which · R ^ is hydrogen atom or an alkyl or aralkyl group such as methyl ,. Is ethyl or benzyl group. ·. . . '. 14. Compounds according to claim 12, 'characterized 009883/1958 by the formula -NR ^ -Z wherein D, A, R ₁ , R ^ and Z have the same meaning as in claims 11 and 12. 15. Compounds according to claim 6, characterized in that that in them two identical or different molecules of monoazo dyes of the general Type of formula. · DN = NA ¹ . where D has the same meaning as above and A ^{1 is} the radical a coupling component, in particular a radical of the formula -A-NR ₁ -R ₂ , via its coupling components through a divalent bridge Z ¹ with no dye character
are connected, where either the dye radicals or the bridge Z carry a radical of the formula -NRh-Z, where R _{2 has} the same meaning as in claim 12. -l6. · Connections.according to claim 10, characterized by the formula ■ NC C = CH-AM ₁ R ₂ • _f γ '' ■ '■. ■ ■ · ■ ■. ■ 009883/1958 wherein A, R, and R _{2 have} the same meaning as in claim and Y is a cyano, carbonamide, carbalkoxy or arylsulfonyl group, and at least one of the radicals R, / IU or Y is the radical of the formula -NR ₂ , -Z contains. 17. Compounds according to claim 9, characterized by the formula '·' · where η is 2 or preferably 1, Rh has the same function interpretation as above and A has an anthraquinone residue with 5 to 5 fused rings which contain one or more other substituents and R ^ the same Has the same meaning as in claim 15. ' 18. Process for the preparation of dyes that of water-solubilizing agents. - Groups are free, as indicated by the fact that you have at least one Amino group bonded fiber-reactive radical Z one with min- · at least one fluorine atom substituted nitrogen-containing Introduces heteroeyclus through coupling or condensation » 009883/1958 19. The method according to claim 18, characterized in that that one introduces the remainder of an s-triazine substituted with at least two fluorate arms. 20. The method according to claim 19 *, characterized in that that the fiber-reactive radical Z is a radical of the formula -G C-X 'I ii where one X is a fluorine atom and the other X is an organic radical or a halogen atom. 21. The method according to claim 20, characterized in that that in the fiber-reactive radical Z one X is a fluorine atom and the other X is a fluorine atom, a chlorine atom, a substituted amino group, an alkoxy group, a hydrocarbon radical or an alkyl mercapto radical. 22. The method according to claims 19 to 21, characterized in that one in the starting dye ent- 009883/1958 holding acylatable amino group with a di- or trifluoro-s-triazine azinylated. 23. The method according to claim 22, characterized in that that the acylating agent used is trifluorotriazine. 24. The method according to claim 22, characterized in that the acylating agent used is monochlorodifluoro s-triazine is used. 25. The method according to claim 19 *, characterized in that that one prepares the dye by coupling and using a coupling component that the fiber-reactive Fluorotriazinyl radical Z contains. 26. The method according to claim 25, characterized in that a coupling component of the formula wherein R, an alkyl group, 'R-, an alkylene group or a group of the formula -alkylene-O-CO-CgHj, -, R ₁ , a hydrogen atom or an alkyl group, is formylated in the para position according to Vilsmeyer and the benzaldehyde formed with 009883/1958 a methylene-active compound of the formula Y-CHp-CW, wherein Y is a cyano, carbonamide, carbalkoxy or arylsulfonyl group is, condensed to the styryl dye or the. Coupling component with a diazonium compound couples to the azo dye. 27. Process for dyeing and printing textiles in particular based on fibers containing hydroxyl, amino, amide and / or ester groups, characterized by the use of the dyes according to claims 1 to 17 » 28. Dyeing process according to claim 25, characterized in that textiles made of synthetic fibers are applied Polyester or polyamide based colors. 29. Dyeing method according to claim 25 *, characterized in that that textiles made from natural fibers based on cotton or wool are dyed. 50. The colored obtained according to claims 25 to 27 Material. 0098S3 / 1958 51. Amines of the formula wherein R ₁ and R _{2 are} each hydrogen atoms or optionally substituted alkyl radicals, ■. . d "is a hydrogen atom, a lower alkyl or alkoxy group, a phenoyloxy or a phenyl mercapto group c " a hydrogen atom, a lower alkyl or alkoxy group, a phenylthio or phenoxy radical, a chlorine or bromine atom, a trifluoromethyl group, an alkylsulfonyl group, preferably a methylsulfonyl group or an optionally alkylated, preferably methylated, acylamino group on the nitrogen atom mean in which the acyl radical is the radical of an organic monocarboxylic acid, such as formic, acetic or butyric acid, a organic monosulfonic acid, such as methane, ethane, benzene, Pyridinecarboxylic or thiophenecarboxylic acid or p-toluene monosulphone . acid or the residue of a carbamic acid or a carbonic acid monoester or monoamids, such as phenoxycarbonyl, methoxycarbonyl, and aminocarbonyl, butylaminocarbonyl or an amino group bonded fiber-reactive s-triazinyl radical with at least one fluorine atom, with the proviso that at least one. • the remainder c ", R'n and Ho a remainder of an amino group. bound srtriazines with 1 to. Has 2 fluorine atoms. 009083/1968 • - ORiGISMAL INSPECTED