DE1293362B - Process for the preparation of polyhydroxyl derivatives of dyes - Google Patents

Description

The present invention relates to the production of new, more valuable, more stable, mostly in aqueous Alkalis and / or water-soluble dye derivatives that contain an organic dye on oxy groups an insoluble, d. H. not real, but at most colloidally soluble high polymer polyhydroxyl compound, However, it does not contain pure cellulose, chemically bound. She concerns before especially the production of such derivatives of polysaccharides, such as starch, tragacanth, locust bean gum, the one high, d. H. over 7% and preferably between 10 and 300% amount of chemically bound dye, based on the proportion of polyhydroxyl compound.

The dye derivatives which can be prepared according to the invention can be obtained by in Water and insoluble in aqueous alkalis, d. H. not real, but at most colloidally soluble Polyhydroxy compounds, with the exception of pure cellulose, with organic dyes or with for Dye formation suitable dye intermediates, which with the oxy groups of the used Polyhydroxy compounds can react to form a covalent bond in aqueous Reacts medium and in the presence of acid-binding agents and, optionally after removal of any unlinked portions of intermediate dye, in the case of intermediate dye these are converted into dyes by coupling or diazotization and coupling or by condensation.

As insoluble, i.e. H. at most colloidally soluble polyhydroxy compounds, which are used here as starting materials Can be used are natural, artificial or fully synthetic polymers with exception to understand pure cellulose, especially nitrogen-free polymer compounds, such as the water- and alkali-insoluble cellulose ethers or esters, d. H. those that z. B. in 1 to 8% sodium hydroxide solution are insoluble like weakly carboxymethylated and weakly phosphonomethylated cellulose, i. H. Reaction products of cellulose and chloroacetic acid or chloromethylphosphinic acid with a Degree of conversion of about 0.04 to 0.4, but preferably about 0.1 (this corresponds to a carboxymethyl group to 10 glucose units); however, insoluble ones are particularly advantageous starting materials Starch, tragacanth and locust bean gum. As organic coloring agents or coloring intermediates, those with the oxy groups of the polyhydroxy compounds mentioned to form a covalent one chemical bond can react, are advantageous in the present process those that are water soluble are used, e.g. B. organic dyes or diazo or coupling components, which, in addition to the reactive grouping, are carboxyl groups or, in particular, sulfonic acid groups exhibit. The reactive groups to be mentioned here are the epoxy groups, Ethylenimine groups, isocyanate groups, carbamic acid aryl ester groups, the propiolic acid amide group, Acrylamino groups, vinyl sulfone groups and especially the labile substituents which are easily cleavable while taking along the pair of binding electrons, e.g. B. aliphatically bonded sulfuric acid ester groups and above all aliphatically bonded sulfonyloxy groups and halogen atoms, in particular an aliphatically bonded chlorine atom.

These labile substituents are expediently in the γ or in the / i position of an aliphatic radical which is bonded to the dye molecule directly or via an amino, sulfonic or sulfonic acid amide group; in the case of the dyes which contain halogen atoms as labile substituents, these exchangeable halogen atoms can also be present in an aliphatic acyl radical, e.g. B. in an acetyl radical, or in ^ -position or in a- and / ^ - position of a propionyl radical or preferably in a heterocyclic radical, ζ. B. in a pyrimidine, but especially in a triazine ring.

The dyes and dye formers expediently contain a halogenated 1,3,5-triazine group, especially a grouping of the formula

- X

-C

C-Z

Cl

wherein X is a nitrogen bridge and Z is a preferably substituted amino group, a substituted one Denotes an oxy or mercapto group or a chlorine atom or an alkyl, aryl or aralkyl group.

Of particular interest is the use of dyes which form the grouping of the formula

_n - 1H ₂ "- 1

—N — C

C-Z

(2)

Cl

contain, in which /; is an integer with a value of at most 4 and Z is the meaning given Has.

A wide variety of organic dyes are suitable for the present process, for example oxazine dyes, triphenylmethane dyes, xanthene dyes, nitro dyes, acridone dyes, Perinone dyes, but especially azo, anthraquinone and phthalocyanine dyes.

From the series of the azo dyes are, for example, disazo or trisazo dyes, but in particular Called monoazo dyes.

From the series of anthraquinone dyes are in particular those from 1,4-diaminoanthraquinone-2-sulfonic acid called dissipative dyes. The manufacture of such and other anthraquinone dyes is described in French patent specification 1,182,124. As suitable phthalocyanine dyes especially those which differ from phthalocyanine sulfonamides may be mentioned derive which have at least two free sulfonic acid groups in the molecule and one group in at least one sulfonamide residue contain, which has at least one labile halogen atom. The manufacture of such dyes is described in French patent specification 1 181249.

Dye intermediates which contain the reactive groups or groupings mentioned, are also largely known.

The inventive reaction of the reactive dyes (so-called reactive dyes) or dye intermediates with the mentioned insoluble, ie not really, but at most colloidally soluble polyhydroxyl compounds is expediently carried out in aqueous suspension, preferably in the presence of inorganic acid-binding agents, such as alkali bicarbonates ^ alkali carbonates, alkali phosphates or especially alkali hydroxides or their mixtures. In many cases it proves to be expedient to first allow the polyhydroxyl compounds to swell for some time in the solution or slurry of the reactive dyes or dye intermediates and then to add lye to the reaction medium with stirring. The reaction is preferably cold, at room temperature or at a moderately elevated temperature, i.e. e.g. B. at 20 to 40 ¹ C made. It is thus possible to produce derivatives with a higher dye content, ie derivatives which contain more than 7 and up to 300% (calculated on the dry weight of the polyhydroxyl compound used) of dye. Depending on the reactive compounds chosen, the reaction can take more or less time; in general, however, a high degree of conversion can be achieved after just one hour with dyes which react well, and after a few hours with dyes which react more slowly.

The resulting products can after completion of the reaction z. B. by adding alcohol or preferably separated from acid and isolated by filtration of the reaction mixture. If you have used dye intermediates, these are preferably after thorough Wash, in order to remove not chemically fixed parts, according to usual methods Condensation or converted into dyes by coupling or diazotization and coupling.

The colored derivatives obtained according to the process are high molecular weight dyes, the dye residues contain chemically bound to oxy groups of a polymer chain, and thus polyhydroxyl derivatives of dyes.

Also the polyhydroxyl derivatives of dyes which can be prepared according to the invention and which are not water-soluble are, but can by appropriate grinding or comminution by means of ball or Vibrating mills or in so-called "attritor mills" or in even more powerful mills in the present an agent such as water or alcohol in which the polyhydroxyl derivatives of the dyes are at most swelling, but not soluble, can be brought into a mostly structureless, very fine form Use e.g. B. allows for spin dyeing of viscose masses.

In the spin dyeing of z. 3. Viscose or copper rayon result in those producible according to the invention Colorants, even if they are water-soluble derivatives, washfast colorations, which in contrast to the usual, z. B. American Dyestuff Reporter, Vol. 45 (1956), pp. 263-271, described pigment colorations have retained transparency and brilliance {avoid the so-called "Bacon shine" effect).

The dyes obtained according to the invention can also be used as pigments for coloring synthetic resins and glass fibers, to which they mostly have excellent adhesive strength, are used will. As the dye content increases, the properties change, and one obtains Products that are mostly in water and / or in aqueous alkalis with the formation of viscous solutions of a colloidal character are soluble. They can be used to produce colored, shaped structures, in particular Fibers, sponges or foils, in particular for mass coloring cellulose foils z. B. in the production of packaging material from cellulose films or for dyeing various Materials are used, which are then compared to the usual, transparent colors resulting dyes colored materials through better fastness properties, in particular better wet fastness properties, while fully preserving transparency and brilliance.

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

example 1

In a mixture of 120 parts of water, 80 parts of sodium chloride and 18.8 parts of the compound the formula

«Ns

HO ₃ S

NH-C

C-NH

SO ₃ H

NH,

Cl

40 parts of wheat starch are stirred in. After stirring for 15 minutes, 30 parts of 30% sodium hydroxide solution are added admitted; stirring is continued until a thick paste is formed. After 24 hours that will solid reaction product crushed, added to 1000 parts of water, Congo acidic with hydrochloric acid placed, filtered off and washed thoroughly with hydrochloric water (1 part by volume of concentrated hydrochloric acid to 100 parts by volume Water).

The filter cake obtained is finely divided into 200 parts of water, the 10 parts of concentrated hydrochloric acid included, registered and at 0 to 10 ° with 2N sodium nitrite solution until the iodine-alkali reaction occurs treated. Then bicarbonate is made alkaline and a solution of 50 parts of 1-benzoylamino-8-oxynaphthalene-3,6-disulfonic acid and 30 parts of sodium bicarbonate in 2000 parts of water. After 5 hours the

Suspension made Congo acidic with hydrochloric acid, filtered and the filter cake thoroughly with hydrochloric acid Water (1 part by volume of concentrated hydrochloric acid to 100 parts by volume of water). Afterward the dye is finely divided and added to alcohol; it .wird is neutralized with sodium hydroxide solution, filtered and the dye derivative was washed with alcohol, dried and, if appropriate, ground. Used in this example in place of 1-Benzoylamino - 8 - oxynaphthalene - 3,6 - disulfonic acid other coupling components are used, so will be different Obtained dyes, e.g. B.

- 3 Coupling component colour 1 HO ₃ S ΥΥ \ ~ NH - CO - CH ₃ orange 4th γν
OH 5 OH 2 λΛ Red orange SO ₃ H 6th OH
I. HO ₃ S-KJsJ-SO ₃ H Red orange HO NH ₂ Dark blue H
A.
H ₃ CC C-OH
Il I ^^
TSl TSl f > ^ T »TT yellow «XN IN V, / OU ₃ H Cl H
A.
H ₃ CC C-OH ι ^{3 ± 1}
TSJ TSJ / \ /> yellow IN IN Γ Γ Ι SO ₃ H

continuation

Coupling component H and HO NH ₂
A / V XT χι / ~ TTO MTT C ) ₃ H SO ₃ Na > colour • orange t Red A.
2/3 H ₃ CC C-OH ITV ~ N = N- <T
1/3 HO ₃ S ~ \ y \ / SO ₃ H ri U INrI v_
M \ \ /
C - NH- <
Il ^v -
N 7 " N ~ \, / ^ ^sc NaO ₃ S — Ιλ / L-SO ₃ Na ^ C ' green Cl NaO ₃ S - / Ύ ^ ν- NH-C
Y ^ _N Cl SO ₃ Na OH ^ C ⁷ SO ₃ H Cl ρ vrtj / y N Il ^ - ·
N
/ / 8th 9

The dyes listed above can be converted into a mostly structureless one by wet milling in alcohol Form that is at least colloidally soluble in water and aqueous alkalis.

Example 2
10 parts of the compound of formula

Coupling components, derivatives with the specified color shades can be obtained.

Example 3

In a suspension of 10 parts of the compound of the formula

Cl-C

NH

SO, H

Cl-C

NH,

C-NH

Il

SO, H

NH,

Cl

are dispersed in 60 parts of water; then 10 parts of locust bean gum and 15 parts of 15 percent by volume Stir in sodium hydroxide solution. After 3 hours the solid reaction mass is broken up into 1000 parts Entered water, neutralized the suspension with hydrochloric acid, filtered and the filter cake thoroughly washed.

By subsequent diazotization and coupling with those given in the table above Cl

10 parts of finely powdered tragacanth are stirred into 60 parts of water. After swelling over 15 parts of 15% strength sodium hydroxide solution are kneaded in overnight. After 3 hours, the solid reaction mass is crushed, added to 1000 parts of water, the suspension is neutralized with hydrochloric acid, filtered and the filter cake is washed thoroughly.

By subsequent diazotization and coupling with those given in the table above Coupling components, derivatives with the specified color shades can be obtained.

909517/603

Example 4 15% sodium hydroxide solution mixed. After one hour

10 parts of weakly carboxymethylated Aspencellu- swelling are 12 parts of finely powdered Na-

loosely (one COOH group per 25 glucose units) trium bicarbonate mixed with the reaction mass.

and 20 parts of sodium chloride are added to 70 parts. After 10 minutes, 4.72 parts of the compound

C-NH- / N-SO ₃ H

ι 'ι

M NT

HO ₃ S ¹ ^ χ ^Ν NH ₂

Cl

registered. After 24 hours, the solid reactor 15 is filtered, washed with 5O ⁽⁾ / pc alcohol thoroughly washed,

tion product is crushed, dried in 1000 parts of water and ground.

worn, the suspension with hydrochloric acid is Congo acidic 5 parts of the reaction product obtained

put, filtered and the filter cake thoroughly with together with 1 part of copper phthalocyanine-3,3 ',

hydrochloric acid water (1 part by volume of concentrated salt 3 ^// , 3 '"- tetrasulfochloride (in powder form) in 25 parts

acid to 100 parts by volume of water). The 20 dimethylformamide slurried. After 15 minutes

Yield, based on the amount of months used, 25 parts of water and 1 part by volume of con-

chlorotriazine intermediate, is 70%. centered ammonia stirred in. At intervals of

By subsequent diazotization and coupling for 3 hours, 1 part by volume is concentrated twice.

with the trated ammonia indicated in the table above was added. After standing over

Coupling components can be derivatives with the 25 night the mass is dissolved in 250 parts of water.

specified color nuances can be obtained. wear the resulting suspension with hydrochloric acid

made Congo sour, filtered and the filter cake

Example 5 with hydrochloric water (1 part by volume concentrated

Hydrochloric acid to 100 parts by volume of water) thoroughly

Washed in a mixture of 80 parts of water, 30 parts. Then the filter cake is in alcohol

15 percent by volume sodium hydroxide solution and 40 parts of Na- slurried, neutralized with sodium hydroxide solution,

trium chloride 20 parts are filtered on a high-speed stirrer and dried.

Wheat starch stirred in. After 30 minutes of swelling, a dark blue colored mass results which

8 parts of 2-chloro-4 - (^ - aminoethyl) -amino- are water-soluble in alcohol after wet grinding

6- (2 ', 5'-disulfophenyl) -amino-l, 3,5-triazine will do well with 35.

the swollen mass mixed. After 20 hours B e i s d i e 1 6 Standing, the mass is crushed into 250 parts

Water, neutralized with 2N hydrochloric acid. In a mixture of 120 parts of water, 80 parts

and sodium chloride and 20 parts of the dye are mixed with an equal volume of ethyl alcohol

puts. The flocculated reaction product becomes 40 of the formula

SO ₁ H

40 parts of wheat starch are stirred in. After len alcohol mixed and in a ball or Stirring for 30 minutes, 30 parts of 30% Na vibration mill are ground until there are products soda lye added; stirring is continued until those are obtained which are soluble in water. To paste arises. After 24 hours the reaction is closed, the alcohol is evaporated and the The mass is added to 1000 parts of water, the resulting dry color product may still be sion made Congo acidic with hydrochloric acid, filtered and subjected to Malsjin dry grinding, the filter residue well with hydrochloric water. For spin dyeing of viscose rayon (1 part by volume of concentrated hydrochloric acid to 100 parts by volume of 10 to 100 parts of a 2 to 10% aqueous share water) washed. Then he is fine 60 solution of the water-soluble dye derivative {je crushed entered in alcohol; it is divided into 1175 parts according to the desired color depth Sodium hydroxide solution neutralized, filtered and the coloring 8.5% viscose xanthate solution, accordingly substance derivative washed with alcohol, dried containing 100 parts of α-cellulose, stirred in, and optionally ground. The mass is stirred for 1/2 hour and for 5

The result is a dark orange-colored preparation, vented under vacuum for 65 to 6 hours, the Z. B. as follows into a water soluble product. Then the viscose mass is converted as for the around can be: 25 parts of the poly-position of viscose yarns usual, by spinning hydroxyl derivative of the dye are pressed with 250 partial nozzles and in a precipitation bath, which contains 120 g / l

96% sulfuric acid, 270 g / l sodium sulphate and 10 g / l zinc sulphate, at a temperature of 45 coagulates.

The resulting threads are stretched by 25% and rotating at 600 rpm Collected spinning pot.

The spinning cake obtained is then in a closed apparatus with circulating Aftertreated liquor, first rinsed for 10 minutes with water at 60 to 75 °, then desulfurized with a solution of 5 g / l sodium sulfite for 20 minutes at 70 °, then

ßend finished with 50 g / l sodium oleate at 50 ° for 10 minutes.

The precipitation and aftertreatment baths are not or only weakly colored.

The result is flawless, washfast and rubfast dyeings of good transparency.

Example 7

In a mixture of 40 parts of water, 10 parts of sodium chloride and 18 parts of the compound of formula

HO NH

NH

HO ₃ S

SOaH

NH,

SO ₃ H

Cl

(used as trisodium salt) 10 parts of wheat starch are stirred in. After stirring for 30 minutes 15 parts of 30% sodium hydroxide solution are added; stirring is continued until a paste is formed. To Standing for 24 hours, the reaction mass is dispersed in 500 parts of water, the suspension with Hydrochloric acid made Congo acidic, filtered and the filter cake with hydrochloric acid water (1 part by volume concentrated Hydrochloric acid to 100 parts by volume of water).

The filter cake is diazotized in a cold (0 to 5 °) bicarbonate-alkaline solution of 6 parts 2-aminobenzene-1-sulfonic acid in 200 parts Entered water and stirred for 4 hours. Then it is acidified to the Congo with hydrochloric acid. The red precipitate is isolated by filtration and, as described above, with hydrochloric water washed. The washed filter cake is dissolved in 200 parts of water, the 10 parts of concentrated hydrochloric acid contained, dispersed and at 0 to 10 "with 1N-Nairium nitrite solution until the iodine-potassium starch reaction occurs offset. Then bicarbonate is made alkaline and a solution of 13 parts of l-benzoylamino-8-oxynaphthalene-3,6-disulfonic acid and 20 parts of sodium bicarbonate in 500 parts of water. After 5 hours the Suspension, as described in Example 1, isolated and processed further.

By varying the diazo and coupling components, z. B. the dyes shown in the following table are produced:

Diazo component p-chloroaniline the same m-toluidine the same Coupling component colour 1 1 - aminobenzene-2-sulfonic acid l-oxynaphthalene-4-sulfonic acid Red 2 the same the same the same l- (2'-naphthyl) -3-methyl- Yellowish red 5-pyrazolone-4 ', 8'-disulfonic acid 3 4-benzoylamino-2,5-dimethoxyaniline l-oxynaphthalene-4-sulfonic acid violet 4th the same l-benzoylamino-8-oxynaphthalene- violet 3,6-disulfonic acid 5 the same l- (2'-naphthyl) -3-methyl- green 5-pyrazolone-4 ', 8'-disulfonic acid 6th 2,5-dimethoxyaniline l-benzoylamine-8-oxynaphthalene- violet 3,6-disulfonic acid 7th the same l-oxynaphthalene-4-sulfonic acid violet 8th the same • l- (2'-naphthyl) -3-methyl- Brown 5-pyrazolone-4 ', 8'-disulfonic acid 9 1-oxynaphthalene-4-sulfonic acid Red 10 1 -Benzoylamino-8-oxynaphthalene- Bluish red 3,6-disulfonic acid 11 l- (2'-naphthyl) -3-methyl- Red 5-pyrazolone-4 ', 8'-disulfonic acid 12th l-oxynaphthalene-4-sulfonic acid Red 13th l-benzoylamino-8-oxynaphthalene- Bluish red 3,6-disulfonic acid 14th l- (2'-naphthyl) -3-methyl- Red 5-pyrazolone-4 ', 8'-disulfonic acid

13 14

Example 8

In a mixture of 30 parts of water, 20 parts of sodium chloride and 5 parts of the dye formula

SO ₃ H OH

NH - CO - CH ₂ CH ₂ Cl

NH

CO - CH ₂ CH ₂ Cl

(used as disodium salt) 10 parts are insoluble Stir in starch. After stirring for 30 minutes, 8 parts of 30% strength sodium hydroxide solution are added; it continue to stir until a paste is formed. After 24 hours the reaction mass is divided into 500 parts Entered water, the suspension made Congo acidic with hydrochloric acid, filtered and the filter residue Washed well with hydrochloric water (1 part by volume of concentrated hydrochloric acid to 100 parts by volume of water). Then it is finely chopped and added to alcohol; it is neutralized with caustic soda, filtered and the dye derivative washed with alcohol and dried.

The result is a dark orange-colored mass which, for. B. by wet milling in alcohol into a water-soluble one Product can be transferred.

The red-yellow dye of the formula can also be converted in the same way

OCH ₃

NH ₂

the blue dye of the formula

SO ₂
NH-CH ₂ CH ₂ Cl

NH ₂

SO ₃ H

SO ₂ -CH ₂ CH ₂ OSO ₃ H

NH-

the red-brown dye of the formula

SO ₃ H

OH

the yellow dye of the formula

N -FCH ₂ - CH - CH ₂ Cl] ₂

H ₃ CC CN = N

Cl

SO, H

the yellow dye of the formula

H ₃ C

= N-C

SO ₂

OH

C-N

C = CH ₃

SO ₂ NH - CH ₂ CH ₂ OSO ₃ H

NH - CH ₂ CH ₂ OSO ₃ H

the yellow dye of the formula

Cl

/ ^c \

Cl-C

Cl

c—

-NH- / V-N = N-C

OH

^ C-N

-C =
CH,

Cl

SO ₃ H

Cl

the yellow dye of the putative formula

Cl

N N

I Il

Cl-C C

Example 9

In a mixture of 30 parts of water, 20 parts of sodium chloride and 3.5 parts of the compound of formula

NH- /> -N = N-C _1-7 J-SO ₃ H

HO ₃ S

N = C = S

OH

10 parts of insoluble starch are stirred in. After stirring for 30 minutes, 8 parts of 30% sodium hydroxide solution are added admitted; stirring is continued until a paste is formed. After 24 hours, the reaction mass is introduced into 500 parts of water; the suspen- Sion is made acidic to the Congo with hydrochloric acid, filtered and the residue on the filter rinsed with hydrochloric water (1 part by volume of concentrated hydrochloric acid to 100 parts by volume of water). Then it will be fine comminuted in 200 parts of water and neutralized with sodium hydroxide solution. Then during a Hour with 200 parts of a 4% strength cold solution of a diazo compound stabilized with zinc chloride OH

fC - N

-C = N
CH ₃

Cl

SO ₁ H

Cl

treated from m-chloroaniline. Then the Solution made Congo acidic, filtered off and washed with hydrochloric acid water. The filter cake will finely chopped in alcohol; it is neutralized with sodium hydroxide solution, filtered and the dye derivative washed with alcohol, dried and ground. A red colored dye results.

Example 10

In a mixture of 30 parts of water, 20 parts of sodium chloride and 2.7 parts of the compound of formula

H ₇ N

SO ₂ -CH ₂ CH ₂ OSO ₃ H

10 parts of wheat starch are stirred in. After 30 minutes of stirring, 8 parts of 30% sodium hydroxide solution are added admitted; stirring is continued until a paste is formed. After 24 hours the reaction mass becomes registered in 500 parts of water, the suspension made Congo acidic with hydrochloric acid, filtered and the filter residue with hydrochloric water (1 part by volume of concentrated hydrochloric acid to 100 parts by volume Water).

909517/603

With a similarly good effect, the coupling components can also be obtained derivatives with the following compound according to the above procedure with the specified color shades. .
Implement strength:

/ CH ₂ CH ₂ OSO ₃ H

H ₂ N ^ N-SO ₂ N

\ y ^ CH ₂ CH ₂ OSO ₃ H

Example 11

In a mixture of 30 parts of water, 20 parts by subsequent diazotization and coupling sodium chloride and 4.7 parts of the compound of with the formula given in the table of Example 1

NH,

HO ₃ S

C-NH

SO ₃ H

10 parts of corn starch are stirred in. After stirring for 30 minutes, 8 parts of 30% sodium hydroxide solution are added admitted; stirring is continued until a paste is formed. After 24 hours the reaction mass becomes registered in 500 parts of water, the suspension made Congo acidic with hydrochloric acid, filtered and the filter cake with hydrochloric water (1 part by volume of concentrated hydrochloric acid to 100 parts by volume Water).

Subsequent diazotization and coupling with those indicated in the table of Example 1 Coupling components, derivatives with the specified color shades can be obtained.

Example 12

35

In a mixture of 30 parts of water, 20 parts of sodium chloride and 3.3 parts of the compound of formula

NH,

CH ₃ OC C

NH

SO ₃ H

Cl

45

50.

10 parts of potato starch are stirred in. After stirring for 30 minutes, 8 parts of 30% sodium hydroxide solution are added admitted; stirring is continued until a paste is formed. After 24 hours the reaction mass becomes registered in 500 parts of water, the suspension made Congo acidic with hydrochloric acid, filtered and the filter residue with hydrochloric water (1 part by volume of concentrated hydrochloric acid to 100 parts by volume Water).

Subsequent diazotization and coupling with those indicated in the table of Example 1 Coupling components, derivatives with the specified color shades can be obtained.

Claims (6)

Patent claims: 1. A process for the preparation of polyhydroxyl derivatives of dyes, characterized in that that one insoluble in aqueous alkalis and in water, d. H. not real, but at most colloidally soluble polyhydroxyl compounds with the exception of pure cellulose with organic dyes or with dye intermediates suitable for dye formation, which with the oxy groups of the polyhydroxy compounds used below Formation of a covalent bond can react, reacts in aqueous medium and in the presence of acid-binding agents and, optionally after removal of any unlinked portions, in the case of dye intermediates these are converted into dyes by coupling or diazotization and coupling or by condensation. 2. The method according to claim 1, characterized in that the polyhydroxy compounds Starch, tragacanth or locust bean gum are used. 3. The method according to any one of claims 1 and 2, characterized in that the fractions of dye or dye intermediate that are not chemically linked to the polyhydroxy compounds washes out. 4. The method according to any one of claims 1 to 3, characterized in that halogenated 1,3,5-triazine compounds as reactive, dyes or dye intermediates capable of forming a covalent bond used. 5. The method according to any one of claims 1 to 4, characterized in that the formed reaction products separated by addition of acid. 6. The method according to any one of claims 1 to 4, characterized in that there is as much Dye or dye intermediate used that derivatives are formed between 10 and contain 300% dye.