DE1619593A1 - Process for dyeing textile materials - Google Patents

Description

Priority 1 June 3, 1966 and May 23, 1967 Great Britain

The invention is directed to a new and improved dyeing process for textile materials and in particular for cellulosic text ilmat er iali en ♦

It has already been proposed to use textile material in particular Cellulose textile materials with dyes, which are reactive Contain Waasstoffatonio, in the presence of alkaline reactive agents and with uncolored polyfunctional compounds, which should be used to achieve a washable fixation " rather, dyes are capable of eu under alkaline conditions dyeing in order to obtain waneoh-resistant dyeings and prints

for well-known unsuppressed polyfuxiktionelle combines "2ie" i _# the effect of a wax-fast fixation of dyes with ramktionable ¥ aee "r-> under active conditions

BAD ORlGJNAL

Substance atoms on cellulose fibers are capable of, are compounds which - two or more nitrogen-bonded CH ₂ β CH CO- groups or two or more nitrogen or oxygen-bonded CH ₂ »CH - SO ₂ groups or at least three, preferably via carbon or Contain phosphorus-bonded ethyleneimine groups or which are capable of forming such groups during deo processes.

It has now been found that textile materials such as "YB. Pipes, threads, threads, flocks, woven and knitted textile materials, be colored and / or printed in a particularly advantageous white can by keeping the material in the presence of an alkaline reacting agent, if necessary at elevated temperature j with at least one uncolored polyfunctional hexahydrotriazine derivative, which under alkaline conditions to effect a wash-proof fixation of reactive hydrogen atoms containing dyes on sellulose fibers, and with treated at least one water-soluble azo dye, which is a or more »preferably via nitrogen, oxygen or Contains sulfur-bonded reactive hydrogen atoms or which is capable of forming the same during the process and which is at least one radical of the formula

- he c — x (1.)

contains, in which X stands for a substituent which is bonded to the triaain nucleus via an oxygen, sulfur or preferably nitrogen atom _f the radical being partly bonded to a carbon atom of the rest of the dye via a nitrogen atom.

9834/17 * 2

The new method can preferably be used for dyeing and / or printing of materials that contain hydroxyl groups are used, i.e. textile materials made of natural and / or regenerated cellulose «, but it can also be used in textile materials from cellulose acetate, from polyacrylonitrile or from Copolymers of acrylonitrile with other vinyl compounds or in the case of textile materials made of linear polyesters, such as z.J ?. Polyethylene glycol terephthalate or textile materials on the Based on terephthalic acid and p-dimethylolcyclohexane and also in the case of textile materials made of natural and / or synthetic Substances are used that contain carbon-guramide groups, such as solid, natural silk or linear polyamides * ·

The dye used in the new method may Example weiee be a disazo dye, ¹ "but .vorzugsweise a Monoazofarbstöff or metal complex, for example, the copper-j chromium or Kobaltkeotplex flonoasafarbatoffs one. To achieve a Wasserlösllchkelt the dye is generally at least" should be a and preferably contain more than one sulfonic acid group, but a variety of other water-solubilizing groups, such as, for example, carboxylic acid, alkyl sulfonic or sulfonic acid groups, can be used instead of or in addition to the sulfonic acid group or the sulfonic acid groups.

The reactive dyes of the above and according to the invention Process types to be used contain one or more reactive hydrogen atoms, preferably about .Nitrogen, oxygen or sulfur are bound, for example in the form of one or more primary or secondary amino groups, "NH groups in heteroeyclic coordination, sulfonamide groups, Sulfonalkylaide groups, such as see p. those with low molecular weight alkyl radicals which can be substituted, Sulfonaryl ainide groups, v / ie e.B. Sulfonylide groups, Carboxylic acid efflid groups, carboxylic acid alkyl arid groups such as e.g. those kit of low molecular weight alkylene or alkyl radicals, Hydroxyl groups and or sulfhydryl groups, the dye The types of particular interest mentioned are those which

0 ^: 0983ft '/ 1? L2-

one or more reactive hydrogen atoms in the form of OTJ-alkylene groups, NH ₂ -alkylene groups, sulfonamide and / or sulfonalkylamide groups with preferably low molecular weight alkyl groups or substituted alkyl groups, such as, for example, dyes containing HgN -SO ₂ groups, HO-CH ₂ -CH ₂ -,

H ₂ E - CH ₂ -, HO - CH ₂ - CH ₂ - NH - SO ₂ -, CICH ₂ CH ₂ NHSO ₂ -, HO ₅ SOCH ₂ CH ₂ NHSo ₂ - and / or H »C - NH - SO ₂ -Groups.

A preferred class of dyes for use in the new processes are those in which at least one substituent the one or more reactive hydrogen atoms contains, is such a substituent that is attached to the nucleus of a Arylaraino group, preferably an anilio group, attached which forms the substituent X in the above formula (1). Such dyes can easily be obtained, for example, by condensation of cyanuric chloride acylatable amino group-containing dye and rait the corresponding substituted arylamine, for example jj-anilnobenzenesulfonamide, p-aminobenzenesulfon-N-raethylamide, p-aminobenzenesulfon-N-fl-aminoethyl amide and p-Aminobenzdlauion-N, N-

di (B-hydroxyethyl) amide.

Examples of usable alkaline reacting agents are inorganic compounds with an alkaline reaction, such as Alkaline tallhy & roaeyd or alkali metal salts of weak Acids, for example sodium carbonate, sodium bicarbonate Sodium Acetate® Disodium Phosphate or Trisodium Phosphate. However, organic alkaline reactants such as pyridine or benzyltrimethylammonium hydroxide can also be used will. Mixtures of two or more alkaline compounds can also be used.

Examples of uncolored polyfunctional resin hydrotriazine derivatives, which are capable of a wash-proof fixation of reactive water-containing atoms under alkaline conditions To effect dyes on Zelluloeefaeern are

009834/1762

Hexahydrotriazine, welcke two or more CHg contain groups bound via nitrogen a ind, or having two or more cHRT CH Soo groups which barren via nitrogen and oxygen are attached above which at least three Äthyleniminogruppen having, if desired, aliphatißche radicals , which are preferably bonded via carbon or phosphorus, or which are capable of forming such groups during the reaction one or more secondary amines are available also belong to this class.

Examples of such compounds are: hexahydro-1,3 »5-trlacryloyl-Si-triazine, hexahydro-1,3,5-triazine (β-ethylaminopropianyl) ~ B« -triazine, hexahydro ^, 3 , 5 -trlsäthylenimino-s-triazln, hexahydro-1,3,5-trivinylsulfonyl-s-triazine and hexahydro-1, ^, S-di-Cß-dialcylaminopropioiiylJ-S-acryloyl-striazine, hexahydro-1,3 / 5-tris / B- (2,3-epoxypropoxy) -propionyljs-triazine. The fixing the dyes to the material to be dyed is possible in the novel process in Raunrteinperatur, that is, at about 15- 30 ⁰ C. However, it is part way in front-to fix the dyes in the methods customary for reactive dyes manner ,, for example by steaming or dry heating to temperatures up to 200 ^° C., provided that the material to be colored and / or printed allows the use of such temperatures. It is advantageous to fix the dyes on the Zellulofletextilmaterial by steaming or by dry heating at 70 to 150 ⁰ C. Within this temperature range, the fixation of the dye is complete in 5 to 10 minutes.

The method according to the invention can be carried out by that one to be colored and / or printed Materlals with the alkaline reacting agent, the dye and the uncolored polyfunctional Hexahydrotriaziiiderivat of the type mentioned above treated consecutively and in any order. However, it is preferred that to be colored and / or

BATH

to treat printing material with a dye liquid or printing paste, which at the same time has an alkaline reaction Agent, the dye and the uncolored polyfunctional part Contains compound of the type mentioned above. The material treated in this way is then rinsed in the usual whiteness, if necessary soaped and finished.

The uncolored polyfunctional compounds are in aqueous solution or together with dispersants and / or protective colloids in finely divided form or as solutions in "water" Miscible solvents used, examples of water-miscible solvents for this purpose are dialkylear-. acid amides, such as dimethylformamide or dimethylacetanide, Lactams such as H-methyl-2-pyrrolidone, ethers such as Clycolether or tetrahydrofuran, and also alcohols such as methanol, ethanol or isopropanol, ketones such as acetone, ' and / or organic acids, such as s.B. Formic acid or acetic acid.

The coloring liquids or printing pastes used in the invention The type used can also be other customary Containing coloring or printing auxiliaries, provided that they do not undesirably blend with the main materials react. Examples of such coloring auxiliaries and / or printing auxiliaries are surface-active compounds such as alkyl sulfonates, or compounds which prevent migration of the dyes, such as s.B. Sodium acetate, or means which improve the solubility and fixation of the dyes, such as urea, or thickeners such as oil-in-water emulsions, Tragacanth thickeners, alginates or methyl cellulose.

As a rule, the dye liquids and printing pastes are used applied to the material to be treated by impregnation, padding or printing »

In general, in the process according to the invention for dyeing » Ben and / or printing of textile materials about 10 to

009834 / 17S2

200 parts of an alkaline reactant "; and approximately 20 to 4Ö0 parts one? uncolored polyfunctional compound of the above-mentioned type for 100 parts of dye each time used.

The dyeings and prints that are obtained by the process according to the invention are superior to those dyeings and ^{prints that are obtained with:} reactive dyes by conventional methods - a considerable improvement lies in the color strength and in the shortening of the time required for fixation and washing. Measurements show that this is due to the fact that a much higher proportion of dye is fixed during the dyeing process.

The invention is explained in more detail using the following examples, in which all parts and percentages are by weight expressed bind unless otherwise noted.

example 1

2, J5 parts (M / 400) of the turoh condensation of cyanuric chloride with 1 mole of trisodium salsa of 2- (2 ^I -sulfophenylazo) -8-amino-1-naphthol-3 _# 6-disulfonic acid and 1 mole of 4 <~ aminob ' enzolaulfondl-K, H .- (fl-hydroxyäthyI) -ami & ₈ obtained dye, 10 parts of urea, 2 parts of hexahydro-1,3,5-triacrylQyl-s ^ triazine, 2 parts of Hatrlumbiearbönfttf 35 parts of 4 ^ hatriuia alginate solution and 49 Parts of the water are smelled by dividing a printing paste. The cloth is dried, dampened 5 min at 102 ⁰ C, then 5 min gewaechen rinsed in water in a boiling aqueous detergent 0 ₉ and dried, the cloth is colored bluish red,

Measurements of the amount of dye washed out confirm that the percentage fixation is in the order of 84 % .

In the following table are. 'The, percentage' 'fixation and

00SS34 / 17S1

BAD0B1Q5MAU

the tare tones indicated with other dyes in a analog mode of operation can be obtained. The compounds of Examples 2 bia 9 are prepared by the codensation of Cyanuric chloride with 1 mole of those mentioned in the third column Aminoazo compound and with 1 mole of the in the second column called amine. In the compounds of Examples 10 to 15, the amount of the aminoazo compound used was one half mole per mole of cyanuric chloride.

009834/1712

example

Amine

Aminoazo compound

hue

Fixation

ο σ «Ο

■■ <*> -

σι ro

p-AsilnobenzoXsuXfonamid

p-Aminobensolsulfön-ßaminoäthylajcid '

p-ABiinobenjBOleulfon-di-N »N- (Ä-hydroxyethyl} -aald

p-Aminobensol8ulfonaaid

dito

dito

dito

2- (2 ^f -Sulfophenylaso) -8-anino-1-naphthol-3 "6-disulfonic acid"

dito

2- (2 ^f - »Sulfophenylaso) -8- ⁿ ( ^w i ^l '8

aJtih-6 ^{? v} -ylainino / -i-naphthol-3 · 6-disulfonic acid

2- (5 ^f -Alaino-2 '-sulfophenylaBO) -8-benzaiBido-1-naphthol-3,6-disulfone acid

2- ( H * -Sulfophenylazo) -6-

amino-l-naphthalene-3-sulfone

acid

Copper complex of 2- (3 ^for chloro-2 * -hydroxy-5 ^f -sulfophenylazo) -8-amino-1-naphthbl-3 »6-disulfonic acid

Copper kpBipiex of 2- / 4 * - (2 "* 5" -Di-SUXfophenyXaso) -5'-ethyl-2'-hydroxyphehylazo / -amino-1-naphthol-3 » 5-disulfonic acid

bXäuXichrot

dito

dito

dito

orange

purple

blue

85 %

92 Ji

91. * ·

90 %

77

82 %

example

Amine

Elderinoazo connection

hue

Fixation

10 15th

p ^ aminobensoleulfonanide

dito

O
O 11th p-amlnobensol sulfone
S-aminoethylaniid CP
OO
U » 12th dito * - 13th p-aminobenzene sulfonamide 762 14th dito

dito Copper complex of 2- £ i »» - (2 ^ll _> 5 ⁿ - 'Disulfophenylaso) -5 * -methyl-2 ♦ -aydyo3Eyphenylaso7 ^ 7- (3 "' -sulfoij« »- eainoanilino) -i-naphthol-3- sulfoneSure

bluish gray

1: 2 cobalt complex of 2- (5 ^f -Hitro- petlich-2'-hydro3EyphenylaBo-8-aeino-l ~ black

naphthol-3 $ 6-dieulf onsfiuro

i: 2C-Chromium complex of 2- (5 ^f -nitro-2 ^f -hydroxyphenylazo) -8-aaino-1-naphthol ^ 3 »6-di8ulfon · sfture

1: 2-Chroiakoinplex of 2- (2 ^f carboxyphenylazo) -6-amino-inaphthol-3-butonic acid

l-Aadno-2,7-01 (5'-amino-2'-sulfophenylazo) ~ 8-naphthol-3 _S 6r-di8-sulfonic acid

69

95

dito 95 % O green loan
sehwara 96 y I. dito
dear-
Brown 94 %
93 % greenish
blue 88.4 %

- 11 -

Example 16

A printing paste was made by mixing together 20 parts of urea, 35 parts of a 4% sodium alginate solution, 2 parts of hexahydro-1,3,5-triacryloyl-a-triazine, 1.5 parts of sodium carbonate, 5 parts (M / 400) of the sodium salts of the 1: 2 chromium complexes obtained by condensation of cyanuric chloride with p-phenylenediaminesulfonic acid (1 mol) and 2- (5 ^f -nitro-2'-hydroxyphenylazo) -Ö-aaiino-1-naphthol-3,6 -diaulfon-acid (1 mol) obtained dye and 37.5 parts of water. The paste was printed on a mercerized Baumwolltüch and the cloth was then baked 5 minutes at 15O ⁰ C and washed out as described in Example!. The cloth was dyed green-loan-schwBXB. The fixation of the dye was of the order of 94 55.

Example 17

A printing paste was prepared by mixing together 20 parts of urea * 35 parts of a 4 £ -igen Hatriunalginatiöeung, 2 parts of hexahydro-1,3, S-triacryloyl-B-triaaint 1,5 files sodium carbonate, 2 parts (M / 400) of the Trinatriuraealzes The dye obtained by condensing cyanuric chloride with T-Amiöo-7- (4 · -eulf eoylphenylexo) -8-naphthol-3,6-TJieulfonic acid and metanilic acid, and 37 parts of water. The Faete is printed on a aerierieiertes Baunivolltuch, and the cloth is then 5 ain at 150 ⁰ C and baked as beech rubbed in Example 1, aueßewaachen "Dae cloth is colored bluish red; the fixation of the dyes is of the order of 97? t «

In the following table, Bind, the percentage fixation and the color shades are given, which are obtained with other dyes in an enalogenous procedure. The dyes were produced by condensation of the amino acid compound indicated in the second column, 1 mol of metanilic acid with cyanuric chloride. ■

BAD 0R! Q5 ^ äAύ

example

Aminoazo compound

Farl ton fixie * -. tion #

18 1- (3 ^l -amino-2 ^l -methyl-5 ^l -sulfo- 'gel phenyl) -4- (4'-sulfamylphenylazo) -5-pyrazolone-3-carboxylic acid

19 1-Amino-7- (4'-methylsulfamylphenylazo) -8-naphthol-3,6-di-sulfonic acid

20 1-Amino-7- (3 ', 5'-dioulfamylphenylazo) -8-naphthol-3,6-disulfonic acid

21 1- (3 ^l * amino-2 ^l -methyl-5 ^f -sulfo- yellow phenyl) -4- (3'-ß-sulfatoethyl-

aulfamylphenylazo) -5-pyrazolone-3-carboxylic acid

■■ 98

bluish 08.5 red; ί

bluish 95

red * ^::

95.5

Example <q 22 - -. \ ■ '■'')', ·

A printing paste was made by mixing together. 20 parts of urea, 35 parts of sodium alginate solution, 2 parts of hexahydro-1,3,5-trlacryloyl-s-triaBin »1.5 parts of sodium carbonate, 2 parts (K / 400) of the trisodium salt produced by the condensation of cyanuric chloride with 4 - KfMethylsulfamylaniline ( 1 mol) and 1-amino-7- (2'-sulfophenylazo) -e ^ ßaphthol-3,6-disulfonic acid (1 mol) prepared dye, and 37.5 parts of Wasöer. The Chamfered is printed on a mercerized cotton cloth, and the cloth is then washed at 150 ⁰ C for 5 minutes and baked as described in Example 1. The cloth is colored bluish red. The fixation of the dye is of the order of 93 Ji.-.

The table below shows the percent fixation and the shades, indicated with other dyes by a similar operation can be obtained. The dyes were obtained by condensation of the amino acid compound mentioned in the third column with cyanuric chloride and subsequent treatment with the amine given in the second column

example

OJ

Aalnoaso connection Hue fixation

23 24

25th

σ 26 co

co '^ ^!

27

-α, στ 28

Aniline-3,5-di-sulfonic acid

N- (ft-hydroxyethyl) ethylenedianine

! - (M-fi-Chloroftthyleulfaeyl) -aniline

dito

H- (NA-SuXfatp-fttliyl-Bulfamyl) -aniline

; . ■ ι

p-Ph * nyl «ndiaiBino-o- • Ulfonic acid l-Amino-7- (2 * -eulfophenylaso) -8-naphthol-3,6-disulfonic acid

i (IM ^ sulfophenyl) «· * - (5 * -aeino-2 * -eulfophenylaso> -5-pyrasolon-3-carboxylic acid

l-Anino-7- (2 ^f -eulfophenylaso> -8 ^ -naphthil-3,6-dieulfonic acid

, ditto ■; ■. ' '' ■ ■ '.. ■■ ■ ■■ ·' ·:

bluish- 95 % red

ditto 92 %

ditto _t 9 * %

yellow 85

bluish - 93 % red

ditto 75 *

co cn co co

Extremely good fixations are possible with the above procedure with the new class. Chromium- and cobalt-containing azo dyes available which contain 1 atom of chromium or cobalt complex bound with 2 'molecules of a monoazo compound, of which each has an araino group which is linked to a radical of the formula

C c

I I

K N

Cl

is substituted, where X represents an arylamino group which carries a sulfamyl substituent with at least one reactive Η atom attached to the aromatic nucleus. Within this range, X preferably represents an anilino radical which bears a sulfamyl substituent with at least one reactive atom, in particular a -IiH.CgH..SO ₂ RHg substituent, while the monoazo compound

preferably the formula

Cl

.L

(CO) OH NR fo \

I ⁿ Il I ⁽²⁾

A - N β N - E - NH - C C X

has, wherein A is a p-thenylene or naphthylene nucleus, E is a naphthylene nucleus with a hydroxyl group in the o-position to the azo group and with at least one sulfonic acid group, and η Hull or 1 1st.

Such dyes can be obtained by reacting 1 mole of cyanuric chloride with 1/2 mole of a metal complex _compound containing 1 atom of chromium or cobalt complex on two molecules of one

00983 4/1752

Monoazo connection bound enthttlti won xlenan both eJj ^ acylieirbare. ^ - Aixiiibisr ^ p ^ aufwe ^ t ^ -.- uniS. ' with f ~ Mol ^ lnea. & cryl «!? ^ amins, which have a 'Su! lfa3! ^! tβ.tib'B ^ tφtusni ^ n "· <mi. ■ t' ^ iti'dB> 3% en's- 'an" - to the aromatic learning' boundGiien! 'capable of reacting ^ H atom; '.

wearing. : Λ,

They reaction can be conveniently carried out by stirring an aqueous suspension of cyanuric chloride, addition of one of the two further Heaktioneteilnehmer, stirring the mixture at about O - imfwesentlichen 1O ⁰ C until the reaction followed by the addition is over, the other reactant and stirring the mixture at a much higher temperature, about 25 to 50 ⁰ C ₄ , until the reaction is over. The reaction is by adding a eüurebindenden agent Neuträlisierung of at u * t "reaction sl <Sh bildendln HGL" facilitate ^ tertj fcur prevent hydrolysis is' b zuzugjebfen there ^ Vörzugti the acid-binding Mittsl mii words n ^ cher ^{1 Oeschwindiglceit,!;} that the pH IITF range: ¥ öii eat is giehialten to 8 ^ lite Parbetoffβ can "öüreti ttblicfeir beispielewelBe be isolated ®rfnhrensweieen ^ are for df © isoltftloHi TOTF ^ aBBerlÖBiliehen Reaktivfarbetoffen ge> is, by ⁵ 'salting x> de ^? by Sprititrooknen of the reaction gtaiachea, in which βϊ '? arbstof ¹ I "has been formed. ^

Hooh another Klaeoe ron colors of special Vert for use with the Pärbeyerfahren invented agent the monoazo dyes of the formula

- K m K - B - SH- C

wherein-ii ^^ uiid Ag Benffölkern ^ d ^ re divides (yori ^v dβn1efh ^^ nβ _ί r min «Bl * & ina 'Sojfc * · group' and% ei ^ antieW minde% ^ tenB"'a-,

00 98 3A Λ

■ BATHROOM

Contains sulfamyl substituents with at least one reactive H atom bonded to the aromatic nucleus, and in which
-B-NH- the remainder of an aminonaphtholsulfona acid coupling component which contains the OH group in o-position to the azo group, or the remainder of an i-aryl-5-pyrazolone coupling component which contains the NH group bonded to the aryl group , especially when B represents a 1-hydroxy-3,6-disulfo-2,8-naphthylene or a 1-hydroxy-3-sulfo-2,6-naphthylene radical.

Such dyes can be obtained by a process which is similar to the process described above for the preparation of a metal complex dye, ie by reacting 1 mole of cyanuric chloride with 1 MbI of an amine of the formula Ag
and with 1 mole of an aminoazo compound of the formula

A ₁ * -ϊ «* ■ - ■ B-KH ₂ ; (5)

but they can also by coupling the diazonium salt of an amine of the formula A ₁ MH ₂ with a naphthol or a pyrazolone of the formula

0-HHA ₂ (4)

be inherited.

The coupling is preferably in neutral, weakly acidic * or weakly alkaline aqueous medium carried out in order to Iyββ the chlorine triasin radicals small.

The following examples explain typical processes for the production of preventive dissolution of dyes.

009834/1752

BATH

- 17 - ^: ■ - ■■■ "-": ■ '"- ■ ■. ^: ;

Example·. 28

A 'neutral solution of 75.9 parts of the 1: 2-0] ιγόγ complex '"' of 1-Ardno-7 ^ (2 ^l -hydroxy-5 ^r -nitroph € nylazo) -8 * sewthol-3 _r ^ dieulfonic acid in water (500 parts) is slowly added to a stirred suspension of 30 parts of cyanuric chloride in 200 parts of acetone and 150 parts of ice water at 0-5 ⁰ G, during which the pH by simultaneous addition of 2G aqueous sodium carbonate solution at 5-5 The mixture is then stirred at pH 6.5-7.0 until the condensation is complete and then poured through a sieve min were added and the pH is as described above, at 6.5 to 7,0gehalten. the temperature is raised to 55-40 ⁰ C and the Geraisch is agitated until the condensation has ended. the cast solution through the sieve then vdrd stirred after the addition of potassium chloride to precipitate the dye at room temperature, whereupon the dye is filtered off and is dried. The dye corresponding to Example 15 in the table above contains 1.05 replaceable chlorine atoms for each azo group.

Example 29

A neutral aqueous solution of 17.9 parts of the trisodium salt of 1- (2 ' _t 4- ⁱ "-dichloro * 3-triazine-6 ^l -ylaniino) -7- (2 ^l -salfophenylazo) -8-naphthol-3, 6-disulfonic acid in 250 parts of water is stirred at 10 ⁰ C, is added followed by aqueous solution of 6.8 parts of 4-ArainobenzolBulfon-di-N, H- (ß »hydroacyäthyl) -amide. The temperature is maintained at 35 to 40 ^° C. and the pH is kept at 6.5 to 7.0 by adding 2N sodium carbonate After the condensation has ended, the dye, which is the dye used in Example 1, is isolated by adding Sala Analysis of the dye is found to contain 0.94 replaceable chlorine atoms for each azo group.

00983A / 1752

Example 50

- 18 -

The dye used in Example 1 can also be as follows Method can be obtained:

To a stirred suspension of 18.5 parts of cyanuric chloride in 150 parts of acetone and 150 parts of ice water at 0-5 ° C, a neutral solution of 31.9 parts of 1-amino-8-naphthol-3 »6-disulfonic acid is slowly added . After a zvirei hours of stirring, the mixture is added a solution of 26 parts 4-Äjminobenzol8ulfon-di-N, ii- (ß-hydroxyethyl) -aniid in water was added, followed by increasing the temperature to 35 to 40 ⁰ C. The pH is then slowly increased to 4 by the addition of 2N sodium carbonate and maintained at 4 until the condensation is over. The pH is then increased to 6 to 7, and a suspension of the diaaoniurasalt, which has been prepared in the usual manner from 10.9 parts of orthanilic acid, is added. The pH is maintained at 6 to 7 until the coupling is complete and the dye is isolated by adding salt.

Claims; O Q 9 8 3 4/1752 bad or / gmnal

Claims (11)

Ϊ a te η tan sp iü c h: e 1. A method for dyeing and / or printing textile materials, characterized in that the material is in the presence of an alkaline reacting agent, with at least one uncolored polyfunctional hexahydrotriazine derivative, which under alkaline conditions to cause a wash-proof fixation of reactive hydrogen atoms-containing dyes on cellulose fibers is capable of _f and treated with at least one water-soluble azo dye which contains one or more, preferably bonded via nitrogen, oxygen or sulfur, reactive hydrogen atoms or which is capable of forming the same during the process and which is at least one radical of the formula '. ^: ■■ -.- ■ Γ; - ■, ■ -; ■ '■■■. ■ = ■ "" ■■ . '''':: -. 'Qi. ■. ■ ■. ■ :. ^: '"■■:;. ■■ ■■' .. '■■ -; contains, where I is a substituent attached to the Triaeinkern over an oxygen, sulfur or vorsugaweise Nitrogen atom is bound, with the radical via a nitrogen atom to «in carbon atom of the rest of the dye is bound. 2. The method according to claim 1, characterized in that dafl after treatment with the polyfunctional Hez & nydrotriasinderlvat de «dye and the alkaline smock the style material is subjected to a heat treatment. 00SS34 / 17S2 ν Unteriuyen (Ar ;. 7 j i Abs. 2 Nr. 1 Sok 3 des Ärxtoronetgaa. Ν. 4.9. J967J. 3. The method according to claim 1 or 2, characterized in that the hexahydrotriazine _{derivative used is hexahydro-1 t} j> $ 5-triacryloyl-striazine, 4. Procedure according to one of the preceding «? η claims, thereby characterized in that a cellulosic textile material is used as the textile material. 5. The method according to claim 4, characterized in that the dye is fixed on the textile material by steaming or dry heating to a temperature in the range of 70 "to 15O ⁰ C. 6. The method according to any one of the preceding claims, characterized in that the material ait a dye liquid or a printing paste containing the alkaline reacting agent, the dye and the uncolored polyfunctional compound. 7. The method according to any one of the preceding claims, characterized gekenui · rejects that the dye has one or more reactive Η atoms in hydroxyalkyl «!! -, aminoalkylene, sulfonamide and / or sulfonalkyl aramid groups. β. Method according to one of the preceding claims, characterized characterized in that the As © dye contains at least one substituent which has one or more reactive hydrogen atoms attached to the aromatic nucleus of an arylamino group which forms the substituent X in formula (1) » is or are bound. ' 9. The method according to any one of the preceding claims, characterized characterized in that as a .azo dye or a monoazo dye the metal complex of a monoaza dye is used. . 10. The method according to claim 9, characterized in that a chromium or cobalt-containing dye is used which has 1 atom 009S34 / 17S2 BATH - 21 - ^v Contains chromium or cobalt complex bonded to two molecules of a monoazc compound, each molecule having an amine group having that with a radical of the formula CD Il is substituted in which X is an arylaminogz-group which a sulfamyl substituent with at least one on the aromatic learning bound reactive Η-atom carries " 11. "The method according to claim 9 _P, characterized in that a monomeric dye of the formula A * - "· s M ^CT B" Eq where JL w & ü A _{0 represent} benzoin nuclei, of those © iaer at least eis® SOsH group and the other at least one.SuIfämylsubstituenten with at least one "aminonaphtholeulfonic acid > - bonded to the aromätisehea Έ®τη which "& X & OH-teuppe'in o-steeple sur lmpplTOgsi £ C! 3ip © 2i @ sit (g _ß soft © the IH ° §rupp © to the Ärylgrupp®