DE1949332A1 - Dispersion azo dyes, process for their preparation and their use - Google Patents

Description

TOMS RIVER CHEMICAL CORPORATION, TOMS RIVER, N.J. (UNITED STATES.)

Case TRCC 35

Germany

Dispersion azo dyes, process for their preparation and their Use.

It is known that disperse dyes are used for dyeing various synthetic fibers. the Introduction of so-called "permanent press" - and dirt-repellent Finishing, however, led to higher demands on the fastness properties of the dyeings because of the during finishing existing conditions and the influence of the resins used, which reduces the fastness properties. Since many of the usual j Dyes do not meet these conditions, there is a need for dyes with better fastness properties.

It has now been found that certain azo dyes particularly suitable for dyeing polyester fibers.

The invention therefore relates to dyes of the formula _r which are free from water-solubilizing groups, such as sulfonic acid groups . * 00β82β / 1186

DI = NAN
V

where D is the remainder of a group free of water-solubilizing groups Diazo component, A is an optionally substituted 1,4-phenylene radical, R, an optionally substituted alkyl group, Rp optionally substituted alkylene radical and B an optionally, is substituted radical of the benzoic acid sulfimide.

The dyes are obtained by adding a coupling component of the formula

wherein X is a sulfonyl oxy radical of a sulfonic acid or preferably is a halogen atom, in any order a) with a salt of a benzoic acid sulfimide and b) with the diazonium compound one of water-dissolving groups, such as SuIf © groups, free diazotized diazo component couples.

The dyes of the formula are of interest CO

DN = NtA-NH ₁ -R ₂ -N

where D, A, R ₁ and R ~ mean the same as jDben, and BL a ₍

Is a substituent, in particular a nitro group, a halogen atom,

like a chlorine or Broffiatoffi * a 1,2-benzo or a phonyl group, and η is an integer from 0 to 3 ,. if-.Bl monovalent and n = 0-1 when R-, is benzo.

-3-. ■ 1349332

The dyes of the formula ^d CO ■ are particularly preferred

■ c ^XS ° ²

wherein. D, R, * R ₂ and R_ mean the same as above, and the radical d is a hydrogen or halogen atom, such as a chlorine or bromine atom, a lower alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl - or Buty! group, a lower alkoxy group with 1 to 4 carbon atoms, such as a methoxy, ethoxy, propoxy or butoxy group, a phenylthio or a phenoxy group, a phenyl or cycloalkyl group, or a benzyl or benzyloxy group.

The group c can be as defined for d have and can in addition to the above groups too

a trifluoromethy! group

and, if applicable, on

Nitrogen atom alkylated, preferably methylated acylamino group mean, in which the Äeylrest is the remainder of an organic monocarboxylic acid, such as acetic acid, formic acid, chloroacetic acid or butyric acid, an organic monosulfonic acid such as methane, Ethane or p-toluene monosulfonic acid, or the remainder of a carbamic acid or a carbonic acid monoester such as phenoxy carbonyl, ethoxy carbonyl and butylaminocarbonyl.

/ straight-chain or branched /

The group R ₁ can be a hydrogen atom or a (4iiedere,

i.e. 1 to 4, preferably 2 to 4 carbon atoms containing Al-

how/

kylgruppe, / a methyl, ethyl, n-propyl, iso-butyl or n-

009826 / 188S

Be butyl group, which can be substituted in the usual way, such as a benzyl, ß-phenethyl, cyanoalkyl, such as ß-cyanoethyl or ß- (ß'-cyanoethoxy) -ethyl, alkoxyalkyl, such as ß-methoxyethyl -, 'ß-Ethoxyethyl or 6- methoxybutyl, hydroxyalkyl, such as ß-hydroxyethyl, ß, 7-dihydroxypropyl, nitroalkyl, such as ß-nitroethyl, carbalkoxy, such as β-carbo (methoxy, ethoxy - or propoxy) -ethyl- (whereby the terminal alkyl group in the ω-position can carry cyano, carbalkoxy, acyloxy and amino groups), ß- or * γ- carbo (methoxy- or ethoxy) -propyl-, acylaminoalkyl-, such as ß- (acetyl or pormyl) aminoethyl, acyloxyalkyl, such as ß-acetyloxyethyl, ß-propionyloxyethyl, ß ^ butyryloxyethyl, β, Ύ-diacetoxypropyl, ß- (alkyl or aryl) sulfonylalkyl , such as ß-meth ^ ansulfonylethyl, ß-ethanesulfonylethyl, ß- (p-chlorobenzenesulfonylJ-ethyl, alkyl or arylcarbamoyioxyalkyl, such as ß-methylcarbamyloxyethyl and ß-phenylcarbamyloxyethyl, such as ß-methylcarbamyloxyethyl, alkoxy- , Ethoxy or isopropyloxy) -c arbonyloxyäthyl, 7-acetamidopropyl, aryloxyalkyl, such as phenoxyethyl, ß- (p-nitrophenoxy) -ethyl, ß- (p-hydroxyphenoxy) -ethyl, ß- (ß'-acetylethoxycarbonyl) -ethyl, β- [(β'-cyano, hydroxy, methoxy or acetoxy) ethoxycarbony1] ethyl, cyanoalkoxyalkyl, ß-carboxyethyl, ß-acetylethyl, ß-diethyl-aminoethyl, and ß-benzoyloxyethyl, ß - (p-Alkoxy- or phenoxy-benzoyl) -oxyethy1 group.

Group IL generally contains no more than 18 Carbon atoms. .

The group Rp is an optionally substituted straight-chain one or branched alkylene radical, preferably of the formula

009826/1886

- (CH ₀ ) -, wherein η is a number from 1 to 4; hydroxyl groups in particular come into consideration as substituents.

Of the arbitrary diazotizable amines which are free of water-solubilizing groups and which are suitable as diazo components, are in particular the amines which have a heterocyclic five-membered ring with 2 or 3 heteroatoms, especially one nitrogen atom and one or two sulfur, oxygen or nitrogen atoms as heteroatoms have, such as the benzothiazoles mentioned in US Pat. No. 3,161,631, and aminobenzenes, such as those of the formula _a

-NH ₂

called, where a is a hydrogen or halogen atom, an alkyl or alkoxy, nitro, cyano, carbalkoxy or alkyl sulfone group, b a hydrogen or halogen atom, an alkyl, cyano or trifluoromethyl group and c is a nitro, cyano, carbalkoxy or alkylsulfonyl group mean. Suitable aminobenzenes are listed in U.S. Patent Nos. 3.349.Ο76 and 3.148.178.

Examples are:
2-aminothiazole,
2-amino-5-nitrothiazole,

009826/1835

- ϊ ■■■■■■■■ .- 6 - -

2-Aniino-5-methy lsulfony l-thiazpl, ·

2-Amino-5-cyanthiazole, ·

2-Aπlino-4-methyl-5-nitrothiazole, 2-amino-4-methylthiazole, 2-Amino-4-phenylthiazole, 2-Amino-4 - (^ '- chlorj-phenylthiazole,

2-Amiho-4- (4 ^t -nitro) -phenylthiazole, 3-areopyridine, 3-aminoquinoline, 3-aminopyrazole, -3-amino-l-phenylpyrazole, 5-aminoindazole, 5-amino-l, 2,4- triazole _i 5- (methyl-, ethyl-, phenyl- or benzyl) -l, 2,4-triazole, ^ -amino-1- (4 ^l -methoxyphenyl) -pyrazole, 2-aminobenzothiazole, 2-amino-6- methylbenzthiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-chlorobenzthiazole,

2-Amino-6-cyanobenzothiazole, ■■ "- ..

2-AmInO-O-rhodanbenzthiazole, 2-amino-6-nitrobenzthiazole,

2-AIπino-6-carboethoxybenzthiazole, "■

2-amino- (4- or 6) -methylsulfonylbenzthiazole, 2-amino-1,3,4'-thiadiazole, 2-amino-1,3 »5" thladlazol,

009326 / 1gS5

2-Amino-4-phenyl- or -4-methyl-1,3 * .5-thia-diazole, 2-Amino-5-phenyl-1,3 * 4-thiadiazole, 2-Amino-3-nitro-5-methylsulfony1-thiophene, 2-Amino-3 * 5-bis (methy lsulfony l) -thiophene, S-amino-J-methyl-isothiazole, 2-amino-4-cyano-pyrazole, 2- (4'-nitrophenyl) -3-amino-4-cyanopyrazole, 3- or 4-aminophthalimide,

Aminobenzene, ■

l-amino-4-chlorobenzene, l-amino-4-bromobenzene, l-amino-4-methylbenzene, 1-amino-4-nitrobenzene, l-amino-4-cyanobenzene, l-amino-2,5-dicyanbenzene , 1-amino-4-methylsulfonylbenzene, l-amino-4-carbalkoxybenzene, l-amino-2,4-dlchlorobenzene, l-amino-2,4-dibromobenzene, l-amino-2-methyl-4-chlorobenzene , l-Amino-2-trifluoromethyl-4-chlorobenzene, l-amino-2-cyano-4-chlorobenzene, l-amino-2-carbomethoxy-4-chlorobenzene, 1-amino-2-carbomethoxy-4-ηίtrobenzene, l -Amino-2-chloro-4-cyanobenzene, l-amino-2-chloro-4-nitrobenzene, l-arr.ino-2-bromo-4-nitrob _iff? ^ ^ / 1 ** 5

1-Amino- ^ - chloro-4-carbethoxybenzoi, 1-amino-2-chloro-4-methyl-sulfonylbenzene, 1-amino-2-methyl-sulfony1-4-chlorobenzene, 1-amino-2J ₎ 4-dinitro-6-methylsulf ony! benzene, l-amino-2,4-dinitro-o- (2'-hydroxyäthy! sulfonyl) benzene, l-amino ^^ - dinitro-ö- (2'-chloroethyisulfonyl) benzene, l-amino-2- methyIsulfony1-4-nitrobenzene, l-amino-2-methyIsulfinyl-4-nitrobenzene, l-amino-2,4-dinitrobenzene,, l-amino-2,4-dicyanobenzene, l-amino-2-cyano-4-methyIsulfonylbenzene , l-amino-2,6-diehlor-4-eyanbenzene _a - V

l-Amino-2,6-dlciilor-4-nitrobenzene, ·

l-Amino-2,4-dicyan-6-chlorobenzene, 4-aminobenzoic acid cyelohexy! ester, l-amino-2,4-dinitro-6-chlorobenzene and in particular l-amino - ^ - cyano - ^ - nitrobenzene, l -Aminobenzene-2-, - ^ - or -4-sulfonic acid amides, such as N-methyl- or Ν, Ν-diraethyl- or -dläthylamid, N, 7-IsOPrOPy loxypropyl-2-amino-naphthalene-6-sulfonic aniide, N , * Y ^r -Isopropyloxypropyl-l-aminobenzene-27, -5- or -4-sulfonic acid »amide,

N-Isopropyl-1-ainiiiobenzol-2-, -> - or -4-sulfonic acid amide, N, 'Y-methoxypropyl-1-aiDinobenzol-2-, -3- or -4-sulfonic acid arald, N _J N-bis (3 -hydroxyethyl) -l-aminobenzene-2-, -5- or -4-sulfonic acid amide, 009 8 2 671S ß S

"L-Amino - ^ - chlorobenzene-S-sulfonic acid amide, and the. N-substituted derivatives, 2-, 3- or 4-aminophenylsulphamate, 2-amino-4-, -5- or -6-methylphenylsulphamate, ■. ·

S-Amino-S-niethoxy-phenylsulphamate, ^ -amino-ö-chlorophenylsulphamate, 3-araino-2, β-dichlorophenylsulphalnate, 4-amino-2- or -3-niethoxyphenylsulphamate, N, N-dimethyl-2-aminophenylsulphamate, , N, N-di-n-butyl-2-aminophenylsulfamate, · N ^ N-dimethyl-S-amino - ^ - chlorophenylsulfamate,. N, n-propyl-2-aminophenylsulfamate,. N, N-di-n-butyl-3-aminophenylsulphamate, 0 (3-aminophenyl) -N-morpholine-N-sulphonate, 0 (3-aminophenyl) -N-piperidine-sulphonate, N-cyclohexy1-0- ( 3-arainophenyl) sulfamate, N (N-methylaniline) -0- (3-aminophenyl) -sulfonate, NjN-diethyl - ^ - amino-o-methylphenyl-sulfamate, N-ethyleneimine-O- (4-aminophenyl) - sulfonate, ''..; benzyl-0 (3-arainophenyl) sulfonate and 0-ethyl-0 (4-amino-2 _J 6-dimethyl-phenyl) sulfonate.

4-Aminoazobenzenes, which are used as diazo components

are reversible are e.g. 4-Aminoäzobenzpl, 4-Aιnino-2-nitroazobenzene,

009828/1085

^, ^ '- Dimethyl ^ -aminoazobenzene,' '.

2-methyl-5-methoxy-4-aminoazobenzene,

2,5-dimethoxy-4-aminoazobenzene, - '. '

4'-methoxy-4-aminoazobenzor,

2-Methy1-4'-methoxy-4-aminoazobenzql, j5, 6,4 ■ '-trimethoxy-4-aminoazobenzene,

4 ^r -chloro-4-aminoazobenzene,.

2'- or ^ '- chloro-4-aminoazobenzene,'

3-nitro-4-amino-2 ', 4'-dichlorazobenzene and 4-aminoazobenzene-4'-sulfonic acid amide.

Instead of the above, ionogenic, water-solubilizing agents Groups of free diazo components can also those are used which contain fiber-reactive groups, such as -s-triazinyl radicals, which are 1 or 2 chlorine on the triazine ring or carry bromine atoms, pyrimidyl radicals containing one or two chlorine atoms or one or two arysulfonyl or alkanesulfonyl groups wear on the pyrimidine ring, mono- or bis- (7-halo-ß-hydroxypropyl) -amino groups, ß-Halogenäthylsulfamylreste, ß-Halogenäthoxygruppen, β-haloethyl mercapto groups, 2-chloro-benzthiazolyl-6-azo groups, 2-chlorobenzothiazolyl-6-amino groupsj,. γ-halogen-ß-hydroxy-propylsulfamyl residues, /

Chloroacetylamino groups,
α, ß-dibromopropiony! groups,
Vinylsulfonyl groups or 2, ^ - epoxypropy! Groups.

98 26/1 aas

Suitable fiber-reactive diazo components are, for example, Njß-chloroethyl - ^ - chloro - ^ - amino-benzenesulfamide (hydrochloride), Niß-chloroethyl - ^ - aininobenzene-sulfamide (hydrochloride),. ^ -Bromo - ^ - amino-uj-chloroacetophenone,
Ni'y-chloro-ß-hydroxypropyl - ^ - aminobenzene-sulfamide, N, ß-chloroethyl-1-amino-4-naphthylsulfonamide, Niß-chloroethyl-1-amino-jJ ^ -dichlorobenzenesulfamide and ^ - (7- Chloro-ß-hydroxy-propoxy) -aniline. "

The dyes prepared with such diazo components contain instead of just those present according to the invention fiber-reactive acylamino group Ac is another fiber-reactive group Group whose reactivity can be greater or lesser than that of group Ac

The diazotization of the diazo components 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 nitrosylsulphuric acid in concentrated sulfuric acid.

The coupling can also be carried out in a manner known per se, for example in neutral to acidic agents, if appropriate in the presence of sodium acetate or similar buffer substances or catalysts which influence the coupling rate, such as dimethylformamide, pyridine, respectively. be made the salts thereof, - -

0 0 9 82 6/1 S 8 5

After coupling, all dyes can be removed from the reaction mixture can usually be easily separated off, e.g. by filtering off, as they are practically insoluble in water.

Instead of a coupling component or diazo component, a mixture of several coupling or coupling components according to the invention can be used. Diazo components can be used.

Suitable coupling components, which are preferably used as Starting compounds of the present process are, for example, ■

Ν, β-benzenesulfimidoethyl-N-ethyl-aniline, Ν, β-Benzolsulflmidoäthyl-N-ethyl-m-toluidine, Ν, β-benzenesulfimidoethyl-N-cyanoethyl-aniline, « N, ß- (2,3-naphthalenesulfimidoethyl) -N-ethyl-m-toluidine, and the compounds of the formulas

N CO

CO

^C 2 ^H 4 " ^N \ _SO JXm ₂

'-N. CO

These coupling components are available by calling 009826/18 85

Compound of the formula HA-NR ₁ -Rp-X, in which X is an exchangeable negative radical ', with an alkali salt of a benzenesulfimide, such as N, ß-chloroethyl-N-ethyl-m-toluidine with the sodium salt, of benzenesulfimide, in which the imide hydrogen atom is replaced by a sodium atom. Instead of the N, ß-chloroethyl compounds, you can also use the corresponding ^ ß-hydroxy-7-chloropropyl compounds and other compounds with labile halogen atoms. .

For dyeing, the dyes mentioned are advantageously used in finely divided form, specifically in the presence of one Dispergators, such as sulphite cellulose liquor, or a synthetic detergent, or a combination of-different wetting agents and Dispersants. Before dyeing, the dye is usually in the form of a dye preparation which is a dispersant and contains the finely divided dye or a dye mixture in such a form that when the dye preparation is diluted a fine dispersion is formed with water. Dye preparations of this kind can be made by known methods, e.g. by getting the dyes either dry or wet and without or ground with the addition of a dispersant.

The dyes used according to the invention are special for dyeing according to the so-called thermosetting or padding thermosetting method suitable at which the fabric to be dyed at a temperature which advantageously does not exceed 60 C, with an aqueous dispersion of the dye, optionally in the presence of 1 to 50 $ urea and a thickener, especially sodium alginate, is impregnated. Then will

009826 / iflÖfi

the tissue is squeezed off in the usual way.

The fixation takes place by heating the impregnated fabric to a temperature above 100 ^° C., advantageously to a temperature of 120 to 220 ° C. The fabric is preferably dried before this treatment, for example in a warm air stream.

The new dyes produce yellow to blue colors with excellent light, wash and sublimation fastness properties and very good resistance to acidic and alkaline sweat, very good wet fastness properties and very good rub fastness properties.

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

009826/1885

example

Instructions for the preparation of the coupling components: A mixture of 60 parts of saccharin (sodium salt) and 48 parts of Ν, β-chloroethyl-N-ethyl-m-toluidine is heated to 175-180 ° for 24 hours. The melt is cooled and dissolved in 150 vol. TeHen of hot acetone. The acetone solution is poured into 150 parts by volume of water and stirred for one hour. The product formed is filtered off, washed with water and recrystallized from 100 parts by volume of alcohol. 79 parts of N, $ -benzenesulfimldoethyl-N-ethyl-m-toluidine, melting point 79-8O ^{0 are obtained} .

When using equimolar amounts of the haloalkylanilines listed in the table (column I) and benzenesulfimide salts (Column II) the coupling components indicated in column III are obtained.

II

III

N, ß-chloroethyl-N-ethy 1-aniline

Ν, β-chloroethyl-N-methylaniline

N, ß-chloroethy1-N-butylaniline

N, ß-chloroethyl-N-ethylm-toluidine

Saccharin, sodium salt

SO,

009826/18

N, ß-benzenesulfimidoethyl-N-ethyl-aniline, Pp. 80-81 °.

N, ß-benzenesulfi-

midoethyl-N-me-

ethyl aniline

N, ß-benzenesulfimidoethyl-N-butyl-aniline

N, ß-nitrobenzene

Sulphimidoethyl-N-

ethyl-N-ethyl-ani

^lin I

• »ι ^ .1» 'S- β

ί 8th , - ii I. II SO ₂ . • 1 ^ 49332 Ν, β-chloroethyl-N-ethyl-. ■ ' ^a \ ■ T j III 5 m-toluidine CO ^ Y N, ß-chlorobenzene 9 Ha-N ^ ^{^} Y ^
XI Ct Xl. Il
CO- ^ XJl sulfimido-ethyl-N- Ν, β-chloroethyl-N-ethyl- 2,3-naphthalene-sul- ethyl m ~ toluidine 6th m-toluidine fonimid, Na salt N, ß-chlorobenzene sulfimido-ethyl-N- N, ß-chloroethyl-N-ethy1- ethyl-m-toluidine 7th m-toluidine Saccharin, Na- N, ß- (2V, y-naph- SaIz thalin sulfonimido ethyl-N-äWiyl-m- N ^ -Chlor-pro'pyl-N- Saccharin, sodium salt toluidine ethyl aniline N, ß-Benzolsulfimi ~ ... • dopropyl-N-ethyl- N, ß-chloroethyl-N-ß-cyano- aniline äthy! aniline N, ß-Benz'olsulf irai- doäthy 1-N, ß-cy.an- äthy! aniline

The production of Nitro and Chlorsaecharine is in Beilstein Handbook, Volume XXVII, pages 174 and 175.

The production of naphthalene-2, J-sulfimide is at Kaufmann und Zobel, reports from the German Chemical Society, 1922, no. 6, Dept. B, June 17, 1922, p. 1499.

009820/1885

Example 2.

A solution of nitrosyl sulfuric acid (prepared from 7.2 parts of sodium nitrite and 113 parts of concentrated sulfuric acid) is cooled to 20 ° and treated with 20.7 parts of 2,6 dichloro-4- ^? nitroaniline added. The diazotization mixture is stirred for two hours at 20-25 and then added to a mixture of 260 parts of ice and 200 parts of water.

41.3 parts of Ν, β-benzenesulfimidoethyl-N-ethyl-m-toluidine are added to 100 parts of acetic acid and the mixture within half an hour in the diazonium solution, the temperature was kept at 0-5. The mixture will last two hours kept at 0-5 ° and then poured into a large excess of water. The dye of the formula is obtained by filtering off

Gl CEL 2 4 \ _co

of cellulose acetate and polyester fibers in brown tones dyes with excellent fastness properties *

Example 3. ·

In exactly the same way as in Example 2, 2,6-dichloro - ^ - nitro-aniline is obtained diazotized and with N, ß-benzenesulfimidoethyl N-ethyl-aniline coupled. The dye of the formula is obtained

which cellulose acetate and polyester fibers in yellow cast dyes brown shades with good fastness properties.

Example 4 .; λ

17.3 parts of 2-chloro-4-nitro-aniline are mixed with hydrochloric acid and sodium nitrite are diazotized in the usual way.

41.5 parts of N-ethyl-N ^ ß-benzenesulfimidoethyl-m-toluidine are added to 100 parts of acetic acid. The solution of the diazonium component (Section A) is added to the coupling component within 30 minutes, the temperature being kept at 0 to 5. The mixture is neutralized with sodium acetate, stirred for a further two hours and finally stirred into an excess of water. The precipitated dye is filtered off, washed with water and dried. The dye obtained corresponds to the formula _t

009326/1885

and dyes cellulose acetate and polyester fibers in red tones excellent fastness properties.

Example 5.

2-methylsulfonyl-4-nitro-aniline is diazotized as in Example 2 * 4-1.3 parts of N-ethyl-Njβ-benzenesulfimidoethyl-mtoluidine are added to 100 parts of acetic acid. The coupling component is slowly added to the solution of the diazonium compound at 0 ° to 5 ° over the course of 30 minutes. The mixture is left for 2 hours at the temperature of the ice bath and poured into an excess of water. After filtering off, the dye is washed with water and dried. The dye obtained corresponds to the formula

GH,

and dyes hydrophobic fibers, especially polyester fibers, in bluish red shades with very good lightfastness.

In an analogous manner, the diazo components given in column I and the coupling components given in column II are made Dyes obtained, which polyester fibers in the column III color indicated nuances.

009826/1885

• I) 1

t ι · - - ♦

• ι .-. e a * η * «

'.- 20 -

No. I. II
* ώ I 1 2-amino-6-methylsul-
fonyl-benzothiazole V / Πι Ji ^ / ^ / bluish j
Red , " 2 2-amino-6-methoxy-
benzthiazole ON / ⁰ ^ ⁵ SO Red CH ₃ Vc ₀ A ^ 3 2-amino-benzothiazole / ^C 2 ^H 5 Scarlet fever CH ₃ ^{2 4 N} CO A / 4th 2-amino-6-methyl-
benzthiazole Il reddish J
orange 1 5 2-amino-6-chloro
benzthiazole n- pink { 6th 2-Amino-6-ethoxy ^ -
benzthiazole M.
■ ': - red J 7th 2,6-dichloro-4-ni-
troaniline / HtT
VXIa ₇
CH ₃ ^C 2 ^H 4 ^ _co vü Brown 8th M.
j \ ~ ^ Nj _p h.-n Yj
CH- * -7 ^ GO-S * / Brown 9 «■" -: ■■■■ "-. ■ '■■■' · ■ Brown ': ■■ Y / no · CH ₃ ² I ⁿ CqAx

009826/1885

t · »It

1 ♦ - · I.

It *

- 21 -

2,6-dichloro-4-nitro aniline

2-chloro-4-nitroaniline

2-methylsulfonyl-4-nitro-aniline

II

C _o H

OH ₃ ⁰ A ^

Supreme Court
3

4-nitroaniline

hitrii

-N

<pMi;

-H. 2 4

2 5

l \ αηλ)

III

Brown

Red

Red

violet

orange fiery red

Coloring example:. -

2.5 parts of 2,6-dichloro-4-nitrophenyl-2'-methyl-4 ^f - (N-ethyl-N-ß-benzenesulfonimidoethyl-amino) -l, l'-azobenzene are in a ball mill with 7 * 5 Parts of sorbitol and 50 parts of water are ground to a fine dispersion. * "

The dye dispersion is added to a 0.05 # aqueous sodium alginate solution, which finally contains 5 parts of dye per 1000 parts, and the resulting padding liquor
is brought to the temperature of 25.

The polyethylene terephthalate fabric is then padded with the liquor, squeezed to 65% liquid absorption,
dries in a stream of air "and fixed with dry heat for one minute at 200 °. The fabric is then treated for 5 minutes with a 3 # solution of diisobutylnaphthalene monosulfonic acid (sodium salt), the 5 $
Sodium carbonate contains _t washed at the boil and dried. Man
receives a tan coloration with good structure and good

Claims (8)

Claims. Dyes which are free from water-solubilizing groups Formula R. D-N = N-A-N ^R 2 " ^B where D is the radical of a diazo component free of water-solubilizing groups, A is 1,4-phenylene radical, R _{1 is} an alkyl group, R _{g is} an alkylene radical and B is an optionally substituted radical of benzene sulfimide. 2. Dyestuff according to claim 1, characterized by the
formula D-N =: wherein R, a monovalent substituent or a fused-on
Is 1,2-benzo, and n = 0, 1, 2 or 3 when R 1 is monovalent and n = 0 or 1 when R ^ is benzo. 3. Dyestuffs according to Claims 1 and 2, characterized
by the formula D-N = N- <W- wherein the radical d is a hydrogen or halogen atom, such as a chlorine or Bromine atom, a lower alkyl group containing 1 to 4 carbon atoms, 009826/1885 • I ti like a methyl, ethyl, propyl or butyl group, a lower ' Alkoxy group with 1 to 4 carbon atoms, such as a methoxy, Ethoxy, propoxy or butoxy group, a phenylthio or a Phenoxy group, a phenyl or cycloalkyl group, or a benzyl or benzyloxy radical, and c has one of the meanings given for d may have or also a trifluoromethyl group and an optionally alkylated on the nitrogen atom, preferably mean methylated Äcylamino group in which the Acyl radical is the radical of an organic monocarboxylic acid, such as acetic acid, formic acid, chloroacetic acid or butyric acid, an organic one Monosulfonic acid, such as methane, ethane or p-toluene monosulfonic acid * or the remainder of a carbamic acid or a carbonic acid monoester, such as phenoxycarbonyl, ethoxycarbonyl and butylaminocarbonyl. 009826/1885 .4. Process for the preparation of water-solubilizing agents Groups-free azo dyes, characterized in that one a coupling component of the formula HA-NR ₁ -Rp-XiWOrIn R, an alky! Group, R ₂ an alkylene radical, A a 1,4-phenylene radical and X is a sulfonyloxy radical of a sulfonic acid or preferably is a halogen atom, in any order a) with a salt of a Benzoeäuresulfimiös converts and b) with the Diazoniumver- * binding of one of water-solubilizing groups, such as sulfo groups, free diazotized diazo component couples. , 5. The method according to claim 4, characterized in that the coupling component of stage b) is an aniline of the formula CO HA-NB-R- /
^{1 2} is used in which K is ₃ , a monovalent substituent or a fused-on 1,2-benzo group, and n = 0, 1, 2 or J5 when R 1 is monovalent and n = 0 or 1 when R 1 is benzo . 6. The method according to claim 5 *, characterized in that the coupling component of stage b) is an aniline of the formula ^d CO , "-R ₀ -IT 1 -T-fR-) η
c
used, in which the radical d is a hydrogen or halogen atom, such as a chlorine or bromine atom, a lower alkyl group with 1 to 4 carbon atoms, such as $ ine methyl, ethyl, propyl or butyl group, a lower alkoxy group and 1 to 4 carbon atoms, such as a methoxy, ethoxy, propoxy or butoxy group, a Phenylthio or a phenoxy group, a phenyl or cycloalkyl group, or a benzyl or benzyloxy radical * and c is a can have the meaning given for d or a trifluoromethyl group and optionally alkylated, preferably methylated, acylamino groups on the nitrogen atom, in which the Acyl radical the radical of an organic monocarboxylic acid, such as acetic acid, formic acid, chloroacetic acid or butyric acid, an organic monosulphonic acid, such as methane, ethane or p-toluene monosulphonic acid, or the remainder of a carbamic acid or a carbonic acid monoester, such as phenoxy? -carbonyl, ethoxy carbonyl and butylaminocarbonyl, is. 7. Process for dyeing and printing hydrophobic textile materials. 8. The method according to claim 7 '» characterized in that polyester materials are dyed or printed. O0tS2S / 13SS