DE2557563A1 - DISPERSION-STABLE AQUATIC PREPARATIONS OF DISPERSION COLORS - Google Patents

Description

Our reference: O.Z.31 753 Noe / ah 6700 Ludwigshafen, December 17th, 1975

Dispersion-stable aqueous preparations of disperse dyes

The application relates to aqueous preparations of disperse dyes, which are easy to flow and pour, as well as their use for dyeing synthetic fiber material.

Due to the development and the transition to short dyeing processes are In the last few years the requirements for the finish of disperse dyes have increased considerably. Particularly high The dyeing of wound packages makes demands on the fine distribution and stability of the dispersed dyes in the dye liquor at temperatures in the range from 120 to 140 ° C (so-called HT dyeing process).

Flawless, level winding body dyeings without filtering off the dye have so far only been obtained if preparations are used which contain ligning sulfonates. Since the properties of the individual dyes, such as particle size, particle size distribution, the hydrophilicity, the tendency to crystallize and the solubility in water, differ significantly, is the effect of lignosulfonates is limited to a few dyes.

Another disadvantage of the lignosulfonates is that they contain, for example, fiber material dyeing from linear polyesters, which is particularly annoying with light nuances or brilliant shades.

In addition, lignosulfonates can be reducing under the dyeing conditions act, so that sensitive azo dyes are destroyed and one therefore only reduced more or less strongly during dyeing Color yields achieved.

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Because of the unfavorable properties under the conditions of the HT dyeing process, dispersants come from the groups of Condensation products from naphthalenesulfonic acid and formaldehyde, Cresol or phenol and / or phenol sulfonic acids with formaldehyde or their sulfomethylation products (FIAT Report 101J, pages 1 to 5; DT-OS 20 32 926 and 23 01 638) for such preparations out of consideration.

The object of the present invention was to provide stable, aqueous, finely divided To find preparations of disperse dyes, which the disadvantageous properties of the aqueous preparations of the prior art in the dyeing of wound bodies by the high-temperature dyeing process (HT process) do not have.

It has been found that winding bodies are no matter what the HT process and can dye without dye filtration if aqueous preparations of disperse dyes are used for the preparation of the dyebaths, which

a) 5 * 0 to 55 # O weight percent of one or more finely divided. ter disperse dyes,

b) 10 to 200 percent by weight, based on (a), of a water-soluble surfactants or mixtures of such agents, which by repositioning

α) of di- or polyamines of the formula

H ₂ N - (- RN) _n -H (I),

R ¹
in which R is a linear or branched saturated alkylene

with 2 to 12 carbon atoms, one or two oxygen atoms as

May contain chain links,

R is hydrogen, alkyl with 1 to 6 carbon atoms, hydroxyalkyl

with 2 to 4 carbon atoms or cyclohexyl,

η denote the values 1 to 5 and where in the case of η > 1

R can be the same or different,

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ß) of diamines of the formula

HN-X-NH (II), '2' 2

in which X is methylenecyclopentylene, phenylene or a group of the formula

A ) -C

where A for benzene or saturated cyclohexane rings, the

"5 4 can be substituted by methyl, and Ir and R for

Hydrogen, methyl or ethyl or the group ^ C

stand for a Cyelohexanrest, and mean alkyl with 1 to 4 C-atoms,

2 ^rows

stand for a Cyelohexanrest, and R is hydrogen or

7) of polyethylene imine or polypropylene imine with a degree of polymerization from 5 to 50

or

£) of N, N-bis- (5'-aminopropyl) -propylenediamine- (1,3) with 8 to 550 moles of propylene oxide, butylene oxide or mixtures thereof each Moles of amine and subsequent reaction with so much ethylene oxide that the reaction products, based on the total molecular weight, Have 20 to 80 percent by weight of polyethylene oxide blocks, and reaction .ion of Oxalky1ierungsprodukte with 0.16 up to 1 mole of sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride per molar equivalent of hydroxyl group and subsequent neutralization are obtained,

and

c) 45 to 95 percent by weight of water or a mixture of water and water retention agents and

d) optionally further additives customary in aqueous dispersions,

contain.

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-Jk ο .:

The compositions of the invention are low viscosity dispersions that remain stable and low viscosity both after prolonged storage at 25 to J> 0 C and after several days of storage at 6O ⁰ C. The distribution of pain remains practically unchanged during storage.

The new preparations are outstandingly suitable for dyeing textile material made of synthetic fiber material, in particular of Fiber material made from cellulose esters and, in particular, from those made from linear polyesters or from mixtures of such fibers with Cellulose fibers at temperatures up to 140 ° C.

With the help of the new dye dispersions (preparations) one dye baths in which the dye is stably dispersed and in which the dye - also in the presence otherwise usually Other dyeing agents used - at temperatures up to 140 ° C is not flocculated.

The disperse dyes (a) used are e.g. water-insoluble to sparingly soluble azo dyes, dyes from the series of quinophthalones and their non-water-soluble derivatives, anthraquinone dyes as well as dyes from other classes of compounds that are sparingly soluble in water and that are based on synthetic fibers draw up from an aqueous bath, or consider mixtures of such dyes »

The new preparations according to the invention contain as dispersants water-soluble surfactants (b), which are obtained by reacting first polypropoxylated and / or polyoxybutylated and then polyethoxylated diamines and polyamines of the type mentioned above with sulfur trioxide, chlorosulfonic acid or Sulfopropionic anhydride and subsequent neutralization with bases are obtained. In the case of sulfur trioxide or chlorosulfonic acid the corresponding half-esters of sulfuric acid are obtained, in the case of the anhydride the esters with a sulfonic acid group in the propionyl radical.

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O.Z.

As a rule, 0.16 to 1 sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride is used per mol equivalent of free hydroxyl group at. Since reaction products in which at least 50 # of the free hydroxyl groups are esterified, a particularly high one have a stabilizing effect, preferred surfactants (b) are those obtained by reacting the oxyalkylation products with 0.5 to 1 mole of chlorosulfonic acid, sulfur trioxide or sulfopropionic anhydride per mole equivalent of free hydroxyl group can be obtained.

The polyoxalkylation products are reacted with sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride in on known way. The reaction can advantageously be carried out without a solvent, but in the presence of inert solvents, e.g. anhydrous dioxane, dimethylformamide or aliphatic chlorinated hydrocarbons such as chloroform, carbon tetrachloride or methylene chloride. The reaction with sulfur trioxide or chlorosulfonic acid usually takes place at temperatures between 0 and 25 ° C very quickly. The reaction with the Sulfopropio'.oäureanhydrid expediently takes place at temperatures between 50 and 90, preferably between 60 and 80 ° C. The reactions are generally finished after 0.5 to 5 hours.

For neutralization, i.e. for the production of the salts of the sulfuric acid half-esters or propionylsulfonic acids, the reaction mixture obtained is introduced into aqueous bases. Per mole more applied Chlorosulfonic acid will preferably use about 2 mol, for the other agents about 1 mol, of base. Come as bases preferably the alkali metal hydroxides such as sodium and / or potassium hydroxide, and also organic bases such as aliphatic amines or other bases that form water-soluble salts with sulfuric acid half esters or propionyl sulfonic acids give. When neutralizing, the temperature should be 55 to 40 ° C do not exceed. The neutralization batch is used to isolate the salts concentrated under reduced pressure, first the organic solvent or solvents and then part of the Water to be distilled off. The residue is then expedient

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point to a certain content of active substance (= surface-active Medium) e.g. adjusted by adding water.

The required amount of (b) depends on the one hand on the dye and the concentration of the dye in the preparation and on the other hand on the agent (b) itself. The minimum amount of (b) is 10 percent by weight, based on the dye (a). In general, 10 to 200, preferably 20 to 100 percent by weight (b) are used, based on (a). In preparations with a lower disperse dyestuff content, a somewhat larger amount of (b) will generally be used, based on (a), than in preparations with a higher dyestuff content. In the case of dyes which are difficult to disperse, larger amounts of (b), for example 60 to 100, up to 200 %, based on (a), will be used. The use of even greater amounts than 200 % of (b) then no longer brings any advantages.

Those necessary for the preparation of the surfactants (b) Polyoxalkylation products are made by gradually reacting the amines (α), (ß), (7) and / or (£.) Initially with 8 to 350 Moles of propylene oxide or 1,2-butylene oxide per mole of amine and then Reaction obtained with ethylene oxide. For the reaction, the amount of ethylene oxide is calculated so that the product after the oxethylation 20 to 80, preferably 40 to 70 percent by weight of polyethylene oxide blocks contains. The molecular weights of the addition products are generally between 1000 and 65,000, preferably between 5,000 and 25,000 «Since you get out of conversion products with a Molecular weight between 10,000 and 20,000 particularly effective surface-active agents are the oxyalkylation products Amines with this molecular weight are very particularly preferred.

Oxalkylation products, their content of polyethylene oxide blocks is below 20 or above 80 percent by weight, there are no surfactants effective for the use according to the invention Medium, i.e. a dye dispersion comprising such a medium (b) is no longer sufficient under HT dyeing conditions stabilized.

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The amines of the formulas I and II are, for example, in detail: Ethylenediamine, 1,2-propylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 3-methylaminopropylamine, 3-cyclohexylaminopropylamine, hexamethylenediamine, 2,5- Dimethylhexane-2,5-diamine, 4,9-dioxadodecane-l, 12-diamine, octamethylenediamine-1,8, 6,6-dimethyl-4,8-dioxaundeean-1,11-diamine, bis- (3-aminopropyl ) -methylamine, diethylenetriarain, dipropyl ^ ntriamine, triethylenetetramine, tri-propylenetetramine, tetraethylene pentamine, tetrapropylene pentamine, 1,2-bis (3-aminopropylamino) ethane, aminoethylethanolamine, dihexamethylene triamine; 2-aminomethylcyclopentylamine, l, l-bis- (4-aminophenyl) -cyclohexane, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2,2-bis- (4-aminocyclohexylpropane) , 4,4'-diaminodiphenylmethane, N, N'-dimethyl-4,4'-diaminodiphenylmethane, 3> 5 ^f -dimethyl-4,4'-diaminodiphenylmethane, m- and p-phenylenediamine.

Such come as polyethyleneimines or polypropyleneimines a degree of polymerization between 5 and 50, preferably between 10 and 30 into consideration.

Another aliphatic polyamine is N, N-bis- (j5'-aminopropyl) -propylenediamine-1,3 to call.

The amines used are preferably ethylenediamine, diethylenetriamine, triethylenetetramine, 1,2-propylenediamine, 1,3- propylenediamine, N, N-bis- (3'-aminopropyl) propylenediamine-1,3, 4,4'-diaminodiphenylmethane or Polymin with a degree of polymerization of 10 and 20, since particularly effective surface-active agents (b) are obtained from their alkylene oxide adducts.

The process for preparing the polyalkoxylation products is described, for example, in U.S. Patent No. 2,979,528, or the products are described prepared analogously to the polyalkoxylation process described there.

The addition of the alkylene oxides is advantageously carried out in Presence of acidic or preferably alkaline catalysts the presence or / absence of solvents, as. ■ come ^ avBv Dioxannöderi Dimethylformamide -in-Consider ..The gCePiOlgt preferably under pressure at temperatures

between 11Ö and 150 ° C. -8th-

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QRJGlNAL! NSPECHED

O.ζ. 31 755

The production of the disperse dye preparations according to the invention takes place in a manner known per se by dispersing or homogenizing the disperse dyes (a) in Presence of the water soluble surfactants (b). The disperse dyes can be in powder form or preferably in Form of the press cake obtained in the synthesis can be used.

The dispersion takes place in known size reduction machines such as kneaders, ball mills, dispersers, sand mills, bead mills, or attritors. The dispersing process is ended when the dye has the desired fine distribution. The fine distribution is carried out with the help of the filter test or preferably after the centrifugal test (Richter, Vescia, Melliand Textilberichte, 1965, Issue 6, pages 622 ff).

Additional auxiliaries or additives can be added to the preparations during or after the dispersion, e.g. Water retention agents such as ethylene glycol, diethylene glycol, propylene glycol, Dipropylene glycol or disinfectant.

The following examples are intended to explain the invention further. The parts and percentages given below relate to on weight.

A. Preparation of the water-soluble surfactants (b)

1) The alkylene oxide adducts of the amines were prepared in a known manner by reacting propylene oxide or butylene oxide and the following Reaction with ethylene oxide produced in the presence of basic agents as catalysts.

Per mole of amine, 8 to 350 moles of propylene oxide / butylene oxide and then applied so much ethylene oxide that the reaction product 20 to 80 percent by weight, based on the total molecular weight, Contains ethylene oxide blocks (= adduct).

2) The adduct is then converted into the water-soluble surfactant (b).

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2.1. Half ester of sulfuric acid:

1 mol of adduct from 1) is dissolved in half the amount by weight of anhydrous dioxane. The solution is cooled to 1O ⁰ C to 15 ⁰ C and added dropwise to the calculated amount of chlorosulfonic acid with stirring at 10 or the calculated amount of sulfur introduced in gaseous form. After the addition has ended, the reaction mixture is stirred for a further 1 hour at room temperature.

The mixture is then slowly introduced ^{into 25 percent sodium hydroxide solution at 20 to 40 °} C., the neutralization solution always having a pH value of} · 7 * 5.

In F _a lle derVeresterung with chlorosulfonic acid is therefore approximately 2 moles of sodium hydroxide solution used per mole of chlorosulfonic acid; in the case of sulfur trioxide, one mole per mole of sulfur trioxide is sufficient. The solvent and some of the water are then distilled off from the reaction mixture under reduced pressure at 70 to 80 ° C and the residue is adjusted to an active ingredient content of 30 or 40% Solvents can be used.

2.2. Sulfopropionic acid ester

1 mole of adduct of 1) are heated in half the amount by weight of chloroform or carbon tetrachloride with the calculated amount Sulfopropionsäureanhydrid under an inert atmosphere at 6O ⁰ C and held for 2 to 4 hours, between 60 and 80 ° C. After cooling to room temperature, the reaction mixture is as in 2.1. indicated neutralized and the solvent and some of the water removed.

The water-soluble surfactants (b) produced are shown in the following tables. The means (b) are characterized by the underlying amine; the amounts of propylene oxide or butylene oxide added per mole of amine and of

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Ethylene oxide; the proportion of the attached ethylene oxide in the total molecular weight of the polyoxalkylation product and the per mole Amine originally used, amount of chlorosulfonic acid, sulfur trioxide or sulfopropionic anhydride applied.

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underlying -ΨΡ- 127 Ai.part ■ AS from the Mg "** ■ O.Z. 31 753 2557563 Molequi Amine Table 1 at Mg ⁺ valent - (H Kr. Propylene dioxide 126 total mole 0.167 Mole / hol 78.5 kulargew. Chlorosulfonic acid / 0.5 Amine 126 3 770 Ethylene oxide ti Sulfur trioxide 1.0 Κ, N-BiS- (3'-amino- Ii proportion of dd Moles per mole moles each 0.667 propy1) -propylene- It on Mg ⁺ dd Adduct 0.167 1 diamine-1,3 64 '· 70 18 738 0.5 2 dd •1 4 81 :, dd dd 1 1.0 3 η II II 14 785 dd ti 3 0.667 4th It II ti It Il η 6th 0.167 5 ti 8i It It 70 16 578 4th 0.5 6th dd dd 5 8oo π It dd 1, 1.0 7th Tt dd It 11 575 II dd 3 0.667 8th It dd dd dd dd dd 6th 0.166. 9 dd 98 dd dd 72.5 19 988 4th 0.5 10 ti It 6 380 η dd ti 1 1.0 11 ti dd ti 14,000 Il H 3 1.0 12th If dd dd dd 70 t! 6th 1.0 13th dd 108 2,784 ti 54.7 23 90S 4th 1.0 14th dd II 5 220 H 50 II 1 1.0 15th dd It 6 194 17 340 43.7 Il 3 1.0 16 dd 47 5,974 dd 65 9 972 6th 0.667 17th It 88 4013 It 72.8 12 OO8 6th 1.0 18th ti 105 6 264 7,000 76 12 784 6th 1.0 19th ti 101 6 264 6 600 70 10 958 6th 1.0 20th dd 68 17 890 6 402 80 12 002 6th 1.0 21 K 106 3,526 4,796 70 23 788 6th 0.25 22nd Triethylenetetramine 106 4,960 7 801 70 26 956 4th 1.0 23 H 303 3 600 17 336 dd 60 428 6th 0.5 24 Ethylenediamine 59 ti 20 504 H 6th 0.25 25th 84 dd 42 350 70 6th 1.0 26th η 61 4,350 14 520 η 12 O6O 6th 0.5 27 ^w Π dd 11 730 dd dd 1 0.25 28 π dd It 8 400 70 11 4th 1.0 29 η 74 5 580 ti η 14 560 2 0.25 30th η dd tr dd 4o dd 1 1.0 31 η It 7 5C * 10 150 40 It 4th 1.0 32 η 95 dd 40 18 660 2 1.0 33 η dd 3,300 dd 40 18 660 1 1.0 34 Il 127 4500 13 020 40 12 560 ♦ 1.0 35 η η 4,980 dd 25th 12 56Ο 1 1.0 36 ti 56 10 815 5,000 40 5 56Ο 4th 37 π 76 7 384 It 7 560 4th 1.0 38 Hexamethylenediamine 84 2,200 dd 8 360 4th 39 186 It 3,000 14 500 4th 1.0 40 127 3 320 dd 12 500 4th 41 2-arainomethylcyelopentyl 7 290 3 625 4th 1.0 amine 5,000 dd It 42 4.4 ^! -Diaminodicyclo- 7 302 4th hexy! methane ti ti 43 4,4'-diaminodiphenyl 4th methane ti It 4th dd

⁺ Total molar weight

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underlying -4P * at Mg ⁺ (Continuation) from Mg ⁺ O.Z. 31 753 £ 01 equivalent - 1.0 Amine Table 1 OH 0.33 Mr. Propylene oxide total mole 3 / ODJ 0.66 Mole / mole fraction 580 Ethylene oxide 45 kulargew. 0.33 Amine 5 916 proportion of 70 Chlorosulfonic acid / 0.66 Ethylenediamine It on Mg ⁺ It Sulfur trioxide 0.25 Polymin **
Degree of polymerization D 11 890 40 Mole per mole mole per mole 0.66 44 Il 10 ti It 1 168 Adduct 45 Il 102 14 848 528 Il 19 950 0.18 46 Il Il Il 13 992 ti It 4th 0.36 47 11 205 ti 19 941 4th 0.23 48 Il Il 5,974 . 8 008 70 Il 8th 0.36 49 Polymir. ⁺⁺ 256 ti It It 24 746 4th 0.68 50 Degree of polymerisation 20 It 27 84o 9 898 40 It 8th 51 It It Il It 3 ir 103 It 20 009 8th 52. ti ti 13 992 dd 53 Il 480 Il 46 400 4th 54 dd 18 560 11 8th 55 11 It η 5 It 8th 15th

⁺ Total molecular weight ^{++ polyethyleneimine}

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Tabel

Sulfopropionic acid ester

No underlying
Amine

Propylene oxide
Mol / Mol proportion of Arain in Mg ⁺

Ethylene oxide share % of the Mg ⁺ from the Mg * adduct
Mg ⁺

Sulfopropionic anhydride Mole per mole mole per mole adduct equivalent

OH

101 N, N-bis (3'-amlnopro- 146 8th 500 5 792 40 102 Pyl) -propylenedi It Il 188 ti 103 amine- 1.3 120 7th 000 7th 080 50 O 104 It 120 m 3 634 30th OO 105 Triethylenetetramine 103 6th 000 2 430 30th ro 106 ti 112 6th 500 4th 187 40 107 Diethylenetriamine 86 5 000 2 373 30th O 108 Ethylenediamine 86 Il 3 Il 40 co 109 Il 86 ti o6o 40 110 W. 120 7th 000 7th 150 50 111 dd 74 4th 290 10 70

480

ti

376

268
780

076

290

433

Il

120
500

6 4

6 6 6 4

5 4

3 2

1.0 0.667

1.0

1.0

1.0

0.667

1.0 1.0 0.75 0.5, 1.0

Total molecular weight

V> J

J V

cn cn * -j cn

Table 3

Sulfuric acid half esters

No underlying Amine

Butyloxid Ethylene oxide total moles / moles parts parts % of the Mg amine on the Mg ⁺ on the Mg ⁺ Mg ⁺

Chlorosulfonic acid moles per mole mole per mol adduct equivalent to-

OH

201 Ethylenediamine 30.4 2 190 5 250 70 7th 500 O
co 202 It 103 7th 440 VJl 000 40 12th 500 OO 203 U 59.6 4th 290 10 150 70 14th 500 ex" 204 Trietylene tetram Jui 28.6 2 062 5 250 70 7th 500 O
co
co 205 N, N-bis (3'-aminopropyl-
propylenediamine-1,3 60 4th 312 3 000 40 7th 500

Total molecular weight

4th
4th
4th
6th

1.0 1.0 1.0 1.0

1.0

cn co

O.Z. 31 753

B. Aqueous preparations of disperse dyes

Examples 1 to 35 20 parts of the dye

MH- (CH

0 OH

in the form of the aqueous presscake are ground with 10 parts of the surface-active agent specified in Table I and 60 parts of water until the particle size is below lyum. Milling time and milling unit are given in Table I. Then another 10 parts of the same surfactant are added. The preparations are well finely divided. The fine distribution is indicated in Table I by the spin value according to Richter and Vescia (Melliand Textile Reports 1965 , No. 6, pages 622 ff). The preparations are thin and stable in storage.

Spools dyed with the preparations show level dyeing over the entire bobbin without dye filtering off.

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Table I Example Surfactant Milling Unit Milling Time

Fine distribution ⁺ '

Table 1 No. 1 3

Ball mill tt Hours.

4th
6th

25th
20th

7 10 18

Glass mill

Attritor

Sand Mill Std.

Hours.

Passages

7th
16
10

19th
28

29

19 24

25th

Sand mill passages

18th
31
25th

30 3 * 35

Sand mill, pearl mill

Hours.

14th

16
2

23
31

12 37

13 38 14 39

15 41

16 42

17 43

18 44

19 45

20 46

21 48

22 49

23 51

24 53

25 55

26 Table 2 No. 101

27 103

28 106

29 108

30 111

31 Table 3 No. 201

32 202

33 203 31-204 35 205

1
4th

10
8th
6th

12th

11

11
6th

7th
11

8th
13th

7th
11
10

9
12th

16

13th
18th
14th
18th
17th
12th
17th
20th
15th
18th
10

19th
20th

15th
11
23
12th
18th
19th
17th
20th

22nd
24
31
26th

35
21
37
25th

24
29
17th

27
29
31
14th
24
28
21
27
25th
32

71 64 43 53 41 56 33 51

45 49 38

43 67 40 53 50 44 49 36

Spin value according to Richter and Veseia, Melliand Textile Reports 1965 , page 622 ff.

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Examples 36 to 67 20 parts of the dye of the formula

O.Z.31 753

in the form of the moist press cake with 10 parts each of the dispersant given in Table II and 60 parts of water Grind until the particle size is below lyu. Milling time and milling unit are given in Table II.

Another 10 parts of the corresponding sample are added to the milled samples Dispersant added. The dispersions obtained are thin, storage-stable and result when winding bodies are colored from textured! PES level dyeings without filtration.

The preparations obtained have good fine distribution, which can be seen from the spin distances.

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Dispersants -if- ^ y) 0.7 31 φ
ι 753 57 563 5 14th 30th 51 Table 1 Mr. 2 Table ZI £ < Grinding time c 25th 4th 21 45 30th 4th 6 passages 1 8th 24 67 example 5 Grinding unit dd Ul 16 28 51 3o 9 Sand mill dd Spin value 11 24 30th 35 37 12th If 30 hours 12th 23 32 33 38 13th H tf 10 25th 31 34 39 14th Pearl mill π 8th 12th 30th 50 40 21 It η 9 13th 31 47 41 22nd η IJ 10 23 33 44 42 25th H It 8th 15th 34 43 43 31 ti ti 11 18th 31 40 44 36 It dd 12th 19th 24 45 45 39 ti dd 11 17th 29 43 46 40 η ti 9 21 30th 40 47 41 η η 11 19th 29 41 48 43 η π 12th 22nd 35 31 49 44 π π 8th 12th 18th 62 50 47 η η 9 13th 21 57 51 48 η η 10 16 25th 49 52 50 ! T Il 11 18th 29 42 53 52 η ti 10 17th 21 52 54 53 π It 12th 14th 22nd 52 55 54 η tr 6th 11 18th 65 56 Table 2 tir. 102 M. dd 9 14th 23 54 57 105 η π 12th 20th 29 39 58 107 w rt 11 16 31 42 59 109 Il It 8th 11 33 48 60 110 π π 7th 10 26th 57 61 111 π It 8th 19th 27 46 62 Table 3 No. 202 H Π 8th 17th 24 51 63 204 η ti 9 22nd 36 33 64 205 η ti 65 ΪΤ tf 66 η 67 η

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Examples 68 to 101

25 parts of the dye of the formula

[F / -Ν CH ₀ -CH ₂ -CN O ₀ N- </ \ ^ ² d \ = y \ ch ₂ -CH ₂ OC-CH, "^ Vn = N- <

Cl 0

In the form of the aqueous press cake with 15 parts of the surface-active agent indicated in Table III, 10 parts Ethylene glycol and 50 parts of water are ground until the dispersion is finely divided (particle size <l / um). Grinding unit, grinding time and fine division are listed in Table III.

The preparations obtained are fluid and stable in storage and are very suitable for dyeing wound bodies made of polyester fibers according to the high temperature process.

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· Ν \

surface active
middle Table III Grinding time Fine adjustment 15th 30th 51 Hot example Table 1 No. 1 Grinding unit 6 passages 4th 18th 25th 50 68 6th Sand mills Il 6th 13th 35 47 69 8th 11 11 5 16 30th 47 70 15th dd It 7th 11 41 45 71 16 ft η 3 14th 33 47 72 17th Il η 6th 17th 34 44 73 18th Il η 5. 18th 38 36 74 19th Il 15 hours 8th 11 30th 44 75 20th Glass mill η 10 18th 33 38 76 22nd It 11 11 17th 29 45 77 23 n W. CTl 19th 31 40 78 24 It It 10 15th 30th 48 79 25th Il π 7th 19th 32 40 80 27 η η 9 18th 35 37 81 30th It 30 hours 10 21 33 34 82 33 Attritor π 12th 20th 35 36 83 35 ti It 9 17th 34 38 84 37 If η 11 21 31 38 85 38 η π 10 14th 25th 53 86 39 If 15 hours 8th 19th 27 45 87 41 Pearl mill π CTl 23 34 41 88 44 η η 12th 15th 26th 52 89 45 π π 7th 15th 24 55 90 46 ti ti 6th 12th 29 54 91 50 η ft 5 18th 27 45 92 53 η η 10 11 22nd 61 93 55 ft Il 6th 20th 31 41 ₉ 4 Table 2 no J03 η η 8th 23 36 31 95 304 Il 10 19th 32 40 96 107 dd If CTl 19th 33 36 97 111 η dd 12th 17th 25th 48 98 Table 3 Mr. 201 π π 10 13th 21 59 99 203 H Il 7th 19th 30th 43 100 205 dd Il 8th 101 dd

709 & 28 / Ö994

Claims (8)

Patent claims Stable aqueous preparation of disperse dyes containing a) 5.0 to 55 * 0 percent by weight of one or more finely divided Disperse dyes, b) 10 to 200 percent by weight, based on (a), of a water-soluble surface-active agent or mixtures of such agents, which are obtained by reacting
α) of di- or polyamines of the formula ά ¹ ' (I) in which R is a linear or branched saturated alkylene with 2 to 12 carbon atoms, one or two oxygen atoms as chain links, R can contain hydrogen, alkyl with 1 to 6 carbon atoms, hydroxyalkyl with 2 to 4 carbon atoms or cyclohexyl, η denotes the values 1 to 5 and where η> 1 R can be identical or different, ß) of diamines of the formula HN-X-NH R ² R ² ^ ' in which X is methylenecyclopentylene, phenylene or a group of the formula where A for benzene or saturated cyclohexane rings, the 3 4 can be substituted by methyl, and IHr and R for Hydrogen, methyl or ethyl or the; ^. _Q. ^ R ^ I group "" \ r ^ ρ stands for a cyclohexane radical and R is hydrogen or Mean alkyl with 1 to 4 carbon atoms, γ) of polyethyleneimine or polypropyleneimine with a degree of polymerization of 5 to 50 or 709826/0994 -22- £) of N, N-bis (3'-aminopropyl) propylenediamine (1,3) with up to 350 moles of propylene oxide, butylene oxide or mixtures thereof per mole of amine and subsequent reaction with so much ethylene oxide that the reaction products, based on the total molecular weight - 20 to 80 percent by weight of polyethylene oxide blocks, and reaction of the oxyalkylation products with 0.16 to 1 mol of sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride per mol equivalent of hydroxyl group and subsequent neutralization are obtained,
and c) 45 to 95 percent by weight of water or a mixture of . .Water and water retention agents and d) if appropriate, further additives customary in aqueous dispersions. 2. Preparations according to claim 1, characterized in that the surface-active agent (b) is based on an oxalkylation product with a proportion of 40 to 70 percent by weight of ethylene oxide blocks, based on the molecular weight of the oxalkylation product. 3 «Preparations according to claims 1 or 2, characterized in that (b) is prepared by reacting 0.5 'to 1 mol of sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride per mol equivalent of hydroxyl group in the oxalkylation product and subsequent neutralization, 4, preparations according to claims 1 to 3 * characterized by a content of (b) of 20 to 100 percent by weight, based on (a). 5. Preparations according to claims 1 to 4, characterized in that (b) is a sulfuric acid half ester or sulfopropionic acid ester of an oxyalkylation product which is obtained by oxyalkylating ethylenediamine, diethylenetriamine, triethylenetetramine, 709826/0994 "^2> ■ - Propylenediamine-1,2, propylenediamine-1,2, N, N-bis (5'-aminopropyl) -propylenediamine-1, j5> 4,4'-diaminodiphenylmethane, polymin with a degree of polymerization of 10 or 20 is obtained. 6. Preparations geir ^ i ^! Claims 1 to 5, characterized in that (a) is a dye from the series of the azo dyes, the quinophthalone dyes, the anthraquinone dyes or a mixture of these dyes. 7. A process for the preparation of preparations according to claims 1 to 6 by dispersing the disperse dyes in the presence of dispersants in an aqueous or aqueous / organic phase, characterized in that the dispersant used is a water-soluble surface-active agent or mixtures of such agents, which by reacting α) of di- or polyamines of the formula H N - (- RN) -H (I), R ¹ in which R is a linear or branched saturated alkylene with 2 to 12 carbon atoms, one or two oxygen atoms may contain as chain links, R is hydrogen, alkyl with 1 to 6 carbon atoms, hydroxyalkyl with 2 to 4 carbon atoms or cyclohexyl, η denotes the values 1 to 5 and where in the case η> 1 R can be the same or> different, ß) of diamines of the formula HN-X-NH (II), to In R ² R ² in which X is methylenecyclopentylene, phenylene or a group of the formula where A for benzene or saturated cyclohexane rings, the 709828/0994 ~ ²⁴ ~ ι "5 4 can be substituted by methyl, and B. ^ and R for hydrogen, methyl or ethyl or the group. ^ Fr p stands for a cyclohexane radical, and R is hydrogen or Mean alkyl with 1 to 4 carbon atoms, 7) of polyethyleneimine or polypropyleneimine with a degree of polymerization of 5 to 50
or £) of N, N-bis- (3'-aminopropyl) -propylenediamine- (l, 5) with 8 to 350 moles of propylene oxide, butylene oxide, or mixtures thereof per mole of amine and subsequent reaction with so much ethylene oxide that the reaction products, based on the total molecular weight, Have 20 to 80 percent by weight of polyethylene oxide blocks, and reaction of the oxyalkylation products with 0.16 to 1 mol Sulfur trioxide, chlorosulfonic acid or sulfopropionic anhydride per molar equivalent of hydroxyl group and subsequent neutralization can be obtained. 8. Use of the preparations according to claims 1 to 6 for dyeing textile material which contains synthetic fibers. BASF Aktiengesellschaft 709826/0994