DE2520527C3 - Aqueous preparations of water-insoluble or sparingly soluble dyes or optical brighteners, as well as their production and use - Google Patents

Description

_Q χ, ρ,

Used by printing pastes and other uses in transfer printing, one is called in water insoluble to sparingly soluble dyes use those which, within the scope of this definition, for the Transfer printing processes are suitable, especially dyes, which at atmospheric pressure between 150 and 220 "C transition to at least 60% steam in less than 60 seconds, heat-stable and are transferable without decomposition.

Such dyes are, for example, the 10 (Z = alkyl with 1 to 4 carbon atoms), Monoazo dyes of the formula

NH-Z

O NH ₂ II I

OH

O —R

wherein X and Y are each an alkyl radical having 1 to 4 carbon atoms mean,

OH C-NH

15 O OH (R = alkyl or aryl)

O NH ₂

NO-

H ₁ C

N = N-C

(R = shark)

O OH

0 NH ₂

C ^ = N CH ₃

CO-OR ₁

and

O NH ₂ (R | = alkyl with 3 to 4 carbon atoms),

O NHCH,

NO ₂

XO-CH ₃

CO -NH

N = N-CH
H ₃ C

and above all the quinophthalone dye of the formula γ,

nu
O

60

65

O NHCH,

O NH ₂

OCH,

OFI

and the anthraquinone dyes of the formulas O NH-A (A = alkyl or aryl), as well as the brominated resp.

chlorinated l, 5-diamino-4,8-dihydroxyanthraehinones called.
However, reactive dyes are also suitable,

Cl-CH, - CO - NH-f V-N = N

which can be used in the transfer printing process, such as. B. the dyes of the formulas

OH

CH.

CH,

O ₃ N- <f VN = N ^ f VN

C, H,

C ₂ H ₄ O-CO-CHrCl

Of importance is also the dye selection in la dye combinations, because only Fa ^r bstof ^f e, which are similar in Transfercharaktenstik, should be combined in the transfer process.

The following compound classes in particular are used as optical brighteners that are insoluble to sparingly soluble in water with their non-ionic substitution products into consideration:

a) pyrazolines, such as

1- (4-sulfamoylphenyl) -3- (4-chlorophenyl) -

pyrazoline or
1- (4-methylsulfonylphenyl) -3- (4-chlorophenyI) pyrazoline;

b) coumarins, such as

3-PhenyI-7- (3-methylpyrazoI-1 -yl) -coumarin, 3-PhenyI-7- (3-phenyI-4-methyl-1,2,3-tri-

azol-2-yl) coumarin or
3- (4-Chloro-1,2-pyrazoI-1 -yl) -7- (3-phenyl-4-methyl-1,2,3-triazol-2-yl) -coumarin:

c) mono- and bis-benzoxazoles, such as

Naphthalene-1,4-bis-benzoxazole- (2), thiophene-2.5-bis-benzoxazole- (2), Ethylene-1,2-bis (5-methyl-benzoxazole) - (2), 2- (4-cyanogen y I) -5,6-dimethy! Benzoxazole, 4- (5.7-Dimethylbenzo! <Azol-2-yI) -4'-phenylstilbene:

d) Benzimidazoles, such as

Furan-2.5-bis (N-methylbenzimidazole) - (2);

e) Aryltriazoles, w>

2- (4-chloro-2'-cyano-stilbene-4'-yI) -naphtho- (I ', 2': 4.5) 1.2.3-triazole:

f) naphthoxazoles, such as

2 - ((/) - Styryl) -naphtho- (l, 2-d) -oxazole:

g) Pyrene, like

2-pyrenyl-4,6-dimethoxy-1,3,5-triazine;

h) naphthalimides, such as

4-methoxy-N-methylnaphfhalimid or 4,5-diethoxy-N-methylnaphthalimide;

i) BiS'Aethylene aryls, such as

1,4-bis (2-cyanstyryl- <y) -benzene, 4,4'-bis (2-methoxystyryt-W) -biphenyi.

In addition, it is also possible to use mixtures of different To use Aufhe'leftypen in the context of the definition in the aqueous brightener preparations.

Arii'inäktiv dispersants such. Am Consideration:

30th

35

40

45

55

bO

65 Sulphated primary or s ^ .undare purely aliphatic alcohols, the alkyl chain of which has 8 to 18 carbon atoms, e.g. B. sodium lauryl sulfate, potassium a-methyl stearyl sulfate, sodium tridscyl sulfate, sodium oleyl sulfate, potassium stearyl sulfate or the sodium salts of coconut fatty alcohol sulfates;
sulfated unsaturated higher fatty acids or fatty acid esters, such as oleic acid, elaidic acid or ricinoleic acid, or their lower alkyl esters, e.g. B. ethyl, propyl or butyl esters, and the oils containing such fatty acids, such as olive oil, castor oil. Rapeseed oil;

with the help of an organic dicarboxylic acid, such as maleic acid, malonic acid or succinic acid, but preferably with an inorganic merbasic acid such as o-phosphoric acid or in particular sulfuric acid, addition products of 1 to 20 converted into an acidic ester Moles of ethylene oxide in fatty amines, fatty acids or aliphatic alcohols with 8 to 20 carbon atoms in the alkyl chain, e.g. B. stearylamine, oleylamine, stearic acid, oleic acid, lauryl alcohol, Myristyl alcohol, stearyl alcohol or oleyl alcohol, such as B. the ammonium salt of sulfated lauryl alcohol triglycol ether or from 1 to 5 mol Ethylene oxide on alkylphenols, such as the acidic sulfuric acid ester of the adduct of 2 moles of ethylene oxide in 1 mole of p-nonylphenol, the acidic sulfuric acid ester of the adduct of 1.5 moles of ethylene oxide to 1 mole of p-tert-octylphenol. the acid sulfuric acid ester of the adduct of 5 moles of ethylene oxide with 1 mole of p-nonylphenol, the acidic Phosphoric acid ester of the adduct of 2 mol of ethylene oxide with I Mo! p-nonyiphenol, of the acidic maleic acid ester of the adduct of 2 moles of ethylene oxide with 1 mole p-nonylhenoI;

sulfated ^ esterified polyoxy compounds, e.g. B. suifated, partially esterified polyhydric alcohols, such as the sodium salt of the sulfated monoglyceride of palrnitic acid; instead of sulfates, esters with other polybasic mineral acids, for example phosphates, can also be used;
primary and / or secondary alkyl sulfonates, the alkyl chain of which contains 8 to 20 carbon atoms, e.g. B. ammonium decyl sulfonate, sodium dodecyl sulfonate, sodium hexadecanesulfonate and sodium stearyl sulfonate

10

15th

20th

fonat;

Alkylarylsulfonates, such as alkylbenzenesulfonates with a straight-chain or branched alkyl chain at least 7 carbon atoms, e.g. B. sodium dodecylbenzenesulfonate, 1,3,5,7-telramethyloctylbenzenesulfonate, sodium octadecylbenzenesulfonate; how Alkyl naphlhalin sulfonates, e.g. Nairiurfidibutyinaphthalene sulfonate; or such as dinaphthyl methanesulfonates, e.g. B. the disodium salt of di- (6-sulfonaphthyI-2) methane;

Sulfonates of polycarboxylic acid esters, ζ. Β. Sodium dioctyl sulfosuccinate. Sodium dihexyl sulfophthalate;

the soaps called sodium, potassium, ammonium, N-alkyl, N-hydroxyalkyl, N-alkoxyalkyl or N-cyclohexylammonium or hydrazinium and rviorphoiiniumsaize of fatty acids with 10 to 20 carbon atoms, such as lauric, palmitic, stearic or oleic acid from naphthenic acids, of resin acids such as abietic acid, e.g. B. the so-called rosin soap.

Lignosulfonates and condensation products of aromatic sulfonic acids with formaldehyde have proven particularly advantageous as anionic dispersants proven, such as condensation products from formaldehyde and naphthalenesulfonic acids or from formaldehyde, Naphthalenesulfonic acid and benzenesulfonic acid, or a condensation product of crude cresol, formaldehyde -ind naphthalenesulfonic acid.

But there are also mixtures of anionic dispersants into consideration, such as. B. such from the condensation product of raw cresol, formaldehyde and naphthalenesulphonic acid with ligninsulphonate.

Usually the anionic dispersants are in the form of their alkali salts, their ammonium salts or their water-soluble amine salts. Advantageously, qualities that are poor in foreign electrolytes are to be used will.

AU nirhtinnoffpnp nicnprcriprminpl are called Ηρϊςρϊρίεωρί- se:

Addition products of z. B. 5 to 50 moles of alkylene oxides, in particular of ethylene oxide, where individual ethylene oxide units by substituted epoxies, such as styrene oxide and / or Propylene oxide. can be replaced by higher fatty acids or by saturated or unsaturated Alcohols, mercaptans or amines with 8 to 20 carbon atoms or on alkylphenols or Alkylthiophenols, the alkyl radicals of which are at least 7 Have carbon atoms;

Reaction products from higher molecular weight fatty acids and hydroxyalkylamines. These can be made up, for example, of higher molecular weight fatty acids, preferably those with about 8 to 20 carbon atoms, e.g. B. caprylic acid, stearic acid, oleic acid, and in particular the "under the collective term Kokosölfetisäure" combined mixture of acids and hydroxyalkyl amines, such as triethanolamine or preferably diethanolamine and produce mixtures of these amines, wherein the reaction is so carried out that the molecular there volume ratio between hydroxyalkylamine and fatty acid is greater than 1, e.g. B. 2: 1. Such compounds are described in the American patent

45 script 20 89 212 described;

Alkylene oxide, in particular ethylene oxide, cortification products, whereby individual ethylene oxide units are substituted by epoxides such as styrene oxide and / or propylene oxide, can be replaced; Esters of polyalcohols, especially mono- or Diglycerides of fatty acids having 12 to 18 carbon atoms, e.g. B. the monoglycerides of the lauric, Stearic, palmitic or oleic acid, as well as the fatty acid esters of sugar beetroot, such as sorbitol, Sorbitans and sucrose, for example sorbitan monolaurate palmitate. -stearate, -oleate. -sesquioleat, trioleate or their oxyethylation products.

Fatty alcohol polyglycol ethers have proven particularly advantageous. especially those with more than 20 moles of ethylene oxide have been shown, as evidenced by Cetyi-Stearyiaikohoi with 25 mol of ethylene oxide, stearyl oleyl alcohol etherified with 80 mol of ethylene oxide and oleyl alcohol etherified with 20 to 80 moles of ethylene oxide. Furthermore, phenol ethers, such as p-nonytphenol, are very suitable etherified with 9 mol of ethylene oxide, ricinoleic acid ester with 15 mol of ethylene oxide and hydroabietyl alcohol etherified with 25 moles of ethylene oxide.

These nonionic dispersants should advantageously be low in electrolytes. Mixtures of such agents are possible and have z. T. synergistic effects.

Hydrotropic agents which are used in the aqueous preparations according to the invention are to be understood as meaning those which are capable of converting the dispersion of the water-insoluble or sparingly soluble dyes or optical brighteners into a stable, deflocculated form without a chemical reaction between the dye or the optical brightener and the hydrotropic substance takes place. These compounds should be soluble in water. As substances exhibiting these properties, for. B. contemplated are: hydrotropic salts, such as sodium benzoate, sodium benzene sulfonic acid, n-tnliinkilfnnsaurP ¹ ; Sodium or N-hpn7vkiilfanikan res sodium. In this context, however, nitrogen-containing compounds have proven to be particularly advantageous, such as urea and its derivatives, for example dimethylurea or guanidine chloride. or acid amides, such as acetamide and propionamide and their derivatives, in particular N-methylacetamide.

When using the hydrotropic substance according to the invention in combination with dispersions of dyes according to the definition or optical brightening! becomes a stabilization of the deflocculated dispersion achieved without actually dissolving the dyes

Thanks to this combination according to the invention, namely the anionic and nonionic dispersant together with the hydrotropic agent in the specified amounts, it is possible to obtain aqueous preparations which, on the one hand, are low in dispersant and, on the other hand, are concentrated in dye or optical brightener and which are primarily characterized by its stability at both heat and in the cold in a temperature range of about minus 10 C to plus ⁰ 6O ⁰ C; due to their storage stability of several months; due to the free flow; finely dispersed form and due to their low viscosity in the range of about 10 to 1000cP / 20 ° C.

Due to the high weight proportion of dye or

optical brightener, the aqueous preparations according to the invention are very compact and therefore space-saving. A reduction in storage, dispatch and transport space is therefore guaranteed.

If desired and necessary, these preparations can contain other property-improving additives be added, such. B. hygroscopic agents, z. R. glycols or sorbitol; Anti-rust agents, e.g. B. ethylene glycol, monopropylene glycol; Antimicrobics; Fungicide, ζ. B. aqueous formalin solution; Antifoam agents and viscosity improvers

Due to the presence of about 10% sorbitol, a perfect redispersibility of the completely dried dough can be achieved.

It goes without saying that with brightener preparations only such anionic and non-ionic dispersants or hydrotropic agents are used, which do not have any strongly detrimental properties on the fluorescence of the brighteners (e.g. so-called quenching effects) to have. For later use in Foulardtherm processes These aids must also withstand the short heat loads of 150 to 220 ° C without yellowing.

Thanks to their high content of dye or optical brightener, these preparations are the ones up to now The liquid brands on the market are significantly superior because they are due to their smaller content Dispersants and thickeners for low-viscosity printing inks of sufficient dye or optical properties Let the brightener concentration process. When printing on paper for solvent-free, pure aqueous printing processes using roller, flexographic and, in particular, rotary film printing machines are low in dispersant, highly concentrated preparation systems required. Since paper, compared to textile materials, has a significantly reduced capacity for printing inks, can be used in particular for liefe Shades that are suitable for direct printing on textiles cannot be used.

The new aqueous preparations are produced, for example, by adding the dye

40

Since the preparations according to the invention are low in electrolytes, thickeners can, in contrast to commercially available ones Disperse dyes, also be sensitive to electrolytes. In this context, polyacrylic-based thickeners have proven particularly valuable.

A preferred possible use is also that these dye preparations are used of thickeners for the production of printing pastes on an aqueous basis or on the basis of a water-in-oil emulsion which printing pastes can be used for printing on carrier materials find and which printed carrier materials in turn in the transfer printing process on textile materials can be used.

The new aqueous optical brightener preparations are preferably and advantageously used after dilution with water for the optical brightening of textile materials according to , for example, the exhaust process, high-temperature exhaust process and the Foulardtherm process. If necessary, further suitable dispersants or other auxiliaries can be added to stabilize the liquor and / or to achieve carrier effects.

A wide variety of textile materials can be used as materials, such as B. polyester materials, Polyamide, polyacrylonitrile, cellulose acetate and cellulose triacetate, these materials in the most varied Processing stages may exist. In addition, it is also possible for these preparations to be used for production of printing pastes can be used, which either for the conventional lightening of in particular Find textile materials use, or for printing carrier materials, such as in particular Paper, which in turn is used in the transfer printing process on textile materials.

The brightener preparations can also be added to the spinning mass.

In FR-PS 21 98 983 preparations are already described, which are an anionic and a nonionic Contain surfactant as well as a hydrotropic agent. In this PS, however, only specific anionic

Γι; *. »». «*;» .- »*; *» »! onFrraftik »- * nnH rliiacA u / AtvlAn in o

one of said anion-active and / or non-ionic dispersants mixed and ground what z. B. takes place in a ball mill or sand mill and the remaining components beforehand, during or also only adds after the grinding process, so that a preparation results whose particle size is smaller than 10 μ, in particular smaller than 2 μ.

The new aqueous dye preparations are advantageously used after dilution with Water for dyeing or printing textile materials according to continuous or discontinuous Procedure. Depending on the dyes used in the preparations, the most varied of them can be used Textile materials are dyed or printed, such. B. polyester or cellulose triacetate materials or Fiber mixtures when the preparations are used as disperse dyes.

Preparations are also of interest in the production of printing pastes for traditional textile printing to use with the lowest possible dispersant content, as the disperse dyes available today contain large amounts of dispersant which are washed out after the dye has been fixed « and thus unnecessarily polluting the wastewater.

The amounts used to produce these printing pastes are significantly higher than in the present one Registration used. There is no indication in this PS that a combination of anionic and nonionic dispersants and hydrotropic agents is possible with 0.1 to 5% by weight get along with anion-active dispersant. This brings about when using electrolyte-sensitive thickeners significant benefits.

In the following examples, parts mean parts by weight. The temperatures are given in degrees Celsius.

A. Preparation of the preparations
example 1

500 parts of the coarsely crystalline, dry dye of the formula

NH

O OH

are in a pre-prepared solution of 25 parts

of an anionic dispersing agent (sodium naphthalinsulfonsaures condensed with formaldehyde), 10 parts of a Fettälkoholpolyglykoläthers as nonionic dispersing agent (cetyl / stearyl alcohol etherified with 25 moles of ethylene oxide), 10 parts of 35% aqueous formalin solution, 100 parts of 1,2-propylene glycol as Fröstschutzmitte ¹¹ and 118 parts of Urea as a hydrotropic stabilizer in 147 parts of water with intensive stirring (dissolver or Lödige mixer) slowly added and homogenized and deaerated for about 1 hour,

This 55% mixture of dyestuff is then closed in a sarid bowl or, preferably, in one rien bead mill using Ottawa sand or Siliquafzif balls (I mm diameter) ground for about 10 hours at a temperature of 20 to 50 °. After this After a while, a dispersion is obtained whose overwhelming majority of the particles are smaller than 5 μ. By adding of a further 90 parts of water, if necessary a predetermined weight proportion of carboxy-methylcellulose contains as a thickener to bring the final viscosity into the ideal range of 500 to 1000 cP (Brookfield viscometer; 30 rev / mih.) Will bring the finely ground dispersion is diluted to a dye content of 50% (yield: 1000 parts).

The free-flowing aqueous preparation remains completely unchanged even during a storage period of several months and withstands temperatures from -15 ° to + 40 ° without damage.

Is used instead of the specified dye, the anion-active dispersant, the non-ionic The dispersant and the hydrotropic agent have the same parts as those given in Table 1 below Components, if the rest of the procedure is as indicated, storage-stable, free-flowing aqueous ones are also obtained Dye preparations with analogous properties, their dye content and the respective milling time of the dye is determined and is between 40 and 60 percent by weight or 5 to 10 hours.

Tabel

E.g. dye

No .: ■

Anionaklives
Dispersants Non-ionic
Dispersants Hydrotropes
middle Lignin sulfonate Fatty alcohol polyglycol ether
(Stearyl / oleyl alcohol ver
ether with 80 moles
Ethylene oxide) Acetamide Lignin sulfate Phenolic ethers
(p-Nonylphenol etherified
with 9 moles of ethylene oxide) urea

Condensation product
from about 2 moles of naphthalenesulfonic acid and 1 mole
formaldehyde

Condensation product
Naphthalenesulfonic acid,
Formaldehyde and
Benzenesulfonic acid

Mixture of 6 parts of acetamide

Ricinoleic acid ester with 15 mol
Ethylene oxide with 1 part
Fatty alcohol polyglycol ether
(Etherified cetyl / stearyl alcohol
with 25 moles of ethylene oxide)

Fatty alcohol polyglycol ether
(Oleyl alcohol is etherified with
20 MoI ethylene oxide)

Acetamide

Cl

O NH ₂

OH

CH ₃

Lignin sulfonate

Hydroabietyl alcohol
etherified with 25 moles
Ethylene oxide

Dimethyl urea

O NH ₂

O NH ₂

Mixture of 1 part
Condensation product

and naphthalenesulfonic acid
with 1 part lignin sulfonate

Fatty alcohol polyglycol ether
(Cetyl / stearyl alcohol

VPr-TtJiört jvnf 9 ^ Viol

Ethylene oxide)

Dimethyl urea

continuation

E.g.
No.:

Color SIo (T.

Anion-active
Dispersants

Nichlionogencs dispersant

Condensation product from Felt alcohol polyglycol ether

2 mol naphthalenesulfonic acid (cetyl / stearyl alcohol

and 1 mol of formaldehyde ethereal with 25 mol

(low-salt) ethylene oxide)

(lydrotropcs means

urea

/ "" VC-HN Ö
O

Mixture of dyes (% = wt.%)
Ex. 1 38%
Ex. 2 47.5%
Ex. 3 14.5%

0 NHj

O NH-CH

NH-CH

, CH,

, XH,

^ C H,

Condensation product
from about 2 moles of naphthalenesulfonic acid and 1 mol
formaldehyde

Condensation product
from approx. 2 moles of cre ^ ol,
0.2 moles of 2-naphthol-6-suironic acid and 3 moles of formaldehyde

Poly-2-naphthylmethane sulfonic acid

Felt alcohol polyglycol ether (cetyl / slearyl alcohol etherified with 25 moles of ethylene oxide)

the same

the same

urea

Guanidine chloride

N-methylacetamide

Example 12

500 parts of the dried and powdered presscake of dichloro-indanthrone are dissolved in a solution of 130 parts of urea, 10 parts of sodium dinaphthylmethanesulfonic acid, 20 parts of a condensation product of stearyl / cetyl alcohol with 25 moles of ΔAthulAnrwvH in 100 TC '^ £ ⁿ ^ O ^T1 O ^r * rO ^r * ^{t /} 'e ^r ' ^rT ^ ^/ lcG! 150 parts of water are stirred in and, with the addition of 2000 parts of glass spheres 1 mm in diameter, ground until the particle size is essentially around 1 to 2 microns. Then the preparation is separated from the balls.

A free-flowing storage stick dye preparation is obtained.

Condensation product of naphthalenesulfonic acid and formaldehyde, 20 parts of the reaction product of p-nonylphenol and 9 moles of ethylene oxide, 130 parts Urea, 100 parts of ethylene glycol and 370 parts of 40 water with 2000 parts of sand ground until the Particle size is around 1 to 2 microns, and then from Sd

The result is a pourable, stable dye preparation. Example 14

480 parts of the coarsely crystalline, dry dye of the formula

OH

13th ¹ V ⁰ H
I. H ⁽ C. 500 parts of the crude dye of the formula / ^N \ "N _N / Χ Il example Ϊ C. N 9 S / I. N O

are combined with a solution of 10 parts of a are in a prepared solution of 24 parts 6o of an anion-active dispersant (naphthalenesulfonic acid Sodium condenses with formaldehyde), 10 parts of a fatty alcohol polyglycol ether as non-ionic Dispersant (cetyl / stearyl alcohol etherified with 25 mol of ethylene oxide), 10 parts of 35% aqueous 65 formalin solution, 100 parts of 1,2-propylene glycol as Antifreeze and 124 parts of urea as a hydrotropic stabilizer in 172 parts of water intensive stirring (dissolver or Lödige mixer)

25th

entered slowly and homogenized and deaerated for about 1 hour

The approx. 52% stirring of the dye is then in a sand mill or preferably in a closed pearl mill using Ottawa sand or siliquarzite balls (1 mm diameter) ground for about 10 hours at a temperature of 21) to 50 °. After this Time you get a dispersion, the vast majority of the particles are smaller than 5 μ by adding of a further 80 parts of water, if necessary a predetermined weight proportion of carboxymethyl cellulose contains as a thickener to bring the final viscosity into the ideal range of 500 to 1000 cP (Brookfield viscometer; 30 rpm) to bring the finely ground dispersion is diluted to a dye content of 48% (yield: 1000 parts). the free-flowing aqueous treatment remains even during completely unchanged after several months of storage and withstands temperatures from - 15 ° to + 40 ° without damage.

Example 15

400 parts of the coarsely crystalline, dry dye the formula

NH,

CN

O NH

are in a prepared solution of 20 parts of an anion-active dispersant (naphthalenesulfonic acid Sodium condenses with formaldehyde), 20 parts of a fatty alcohol polyglycol ether as non-ionic Dispersing agent (cetyl / stearyl alcohol etherified with 25 mol of ethylene oxide), 10 parts of 35% aqueous Formalin solution, 100 parts of 1,2-propylene glycol as Antifreeze and 150 parts of urea as a hydrotropic stabilizer in 190 parts of water Intensive stirring (dissolver or Lödige mixer) slowly added and for about 1 hour homogenized and deaerated

This 45% dye mixture is then mixed in a sand mill or, preferably, in a closed one Pearl mill using Ottawa sand or silica quartzite balls (1 mm diameter) for approx. 10 hours ground at a temperature of 20 to 50 °. After this time, a dispersion is obtained, the predominant part of which Most of the particles are smaller than 5 μ by adding another 110 parts of water, if necessary one Pre-determined percentage by weight of carboxymethyl cellulose as a thickening agent, in order to achieve the final vis ^ Bring viscosity into the ideal range of 500 to 1000 cP (Brookfield viscometer; 30 rpm) the finely ground dispersion is diluted to a dye content of 40% (= 11,000 parts). The free flowing Aqueous preparation remains completely unchanged even after several months of storage and maintains temperatures from - 15 ° to + 40 ° without damage,

Example 16

482 parts of the coarsely crystalline, dry dye of the formula

O NH-CH ₃

O NH-CH ₃

are in a pre-prepared solution of 20 parts

": _.""":! ..: .., »_ r \ '.. —-> ——: *> ——: **, ■,!. ■ i- ~ -li ι; ir

ciiica aiiiuiiurtu vuii L / iapngit ,! 1111111.1: 1 ^ ucifjiiiiiaiiiiauiiuil acidic sodium condensed with formaldehyde), 15 parts of a fatty alcohol polyglycol ether as a non-ionic dispersant (cetyl / stearyl alcohol etherified with 25 moles of ethylene oxide), 10 parts of 35% propylene glycol parts as an anti-freeze solution of 1.2% urea, 100 parts as an anti-freeze hydrotrope * stabilizer in 145 parts of water with intensive stirring (dissolver or Lödige mixer) slowly added and homogenized and deaerated for approx. 1 hour.

This 54% dye mixture is then used in a sand mill or preferably in a closed bead mill using Ottawa sand or siliquarzite balls (I mm diameter) ground for about 10 hours at a temperature of 20 to 50 °. After this After a while, a dispersion is obtained whose overwhelming majority of the particles are smaller than 5 μ. By adding from another 108 parts of water, one if necessary Pre-determined percentage by weight of carboxymethyl cellulose as a thickening agent to achieve the final viscosity in the ideal range of 500 to 1000 cP (Brookfield viscometer; 30 rpm) the finely ground dispersion on the dye content

diluted by 48.2%. The free-flowing aqueous treatment remains completely unchanged even after several months of storage and maintains temperatures from - 15 "to + 40 ° without damage.

Example 17

150 parts of a yellow dispersion according to Example 14, 350 parts of a red dispersion according to Example 1. 300 parts of a blue dispersion according to Example 15

and
200 parts of a blue dispersion according to Example 16

are homogenized in a stirred tank.

1000 parts of a black formulation are produced which have a viscosity in the range from 500 to 1000 cP (Brookfield viscometer; 30 rpm).

The free-flowing, highly concentrated aqueous dough remains completely even during a storage period of several months unchanged and withstands temperatures from -15 ° to + 40 ° without damage.

030 262/168

Example 18

445 parts of the coarsely crystalline, dry dye of the formula

O NH ₂

O NH

are in a prepared solution of 10 parts of an anion-active dispersant (naphthalenesulfonic acid Sodium condenses with formaldehyde), 20 parts of a fatty alcohol polyglycol ether as non-ionogenic Dispersing agent (cetyl / stearyl alcohol etherified with 25 Mo! Ethylene oxide), 10 parts 35% aqueous Formalin solution, 100 parts of 1,2-propylene glycol as Antifreeze and 137 parts of urea as a hydrotropic stabilizer in 205 parts of water Intensive stirring (dissolver or Lödige mixer) slowly added and for about 1 hour homogenized and deaerated.

This 48% dye mixture is then stirred in a sand mill or, preferably, in a closed one Pearl mill using Ottawa sand or silica quartzite balls (1 mm diameter) for approx. 10 hours ground at a temperature of 20 to 50 °. After this time, a dispersion is obtained, the predominant part of which Majority of the particles is smaller than 5 μ. By adding another 73 parts of water, add one if necessary Pre-determined percentage by weight of carboxymethyl cellulose as a thickening agent to achieve the final viscosity in the ideal range of 500 to 1000 cP (Brookfield viscometer; 30 rpm) the finely ground dispersion is diluted to a dye content of 44.5% (= 1000 parts). The free flowing Aqueous preparation remains completely unchanged even after several months of storage and maintains temperatures from - 15 ° to +40 "without damage.

Example 19

415 parts of the coarsely crystalline, dry dye of the formula

NH,

CH,

NH,

are in a prepared solution of 5 parts of an anion-active dispersant (naphthalenesulfonic acid Sodium condenses with formaldehyde). 20 parts of a fatty alcohol polyglycol ether as non-iono ^ Genes dispersant (cetyl / stearyl alcohol etherified with 25 mol of ethylene oxide), parts of 35% aqueous Formalin solution, 100 parts of 1,2-graft glycol as Antifreeze and 150 parts of urea as hydrotropes Slabilizer in 222 parts of water with vigorous stirring (dissolver or Lödige mixer) entered slowly and homogenized and deaerated for about 1 hour.

This 45% dye mixture is then ground in a sand mill or preferably in a closed bead mill using Ottawa sand or siliquarzite balls (1 mm diameter) for about 10 hours at a temperature of 20 to 50 °. After this time, a dispersion is obtained, the majority of the particles of which are smaller than 5 μ. By adding a further 78 parts of water, which if necessary contains a pre-determined percentage by weight of carboxymethyl cellulose as a thickener, to bring the final viscosity into the ideal range of 500 to 1000 cP ( Brookfield viscometer; 30 rpm), the finely ground dispersion is diluted to a dye content of 41.5% (= 1000 parts). The free-flowing aqueous preparation remains completely unchanged even after several months of storage and withstands temperatures from -15 ° to + 40 ° without damage.

Example 20

500 parts of the pure dry Wirksubstar.z des optical brightener of the formula

are in a solution of 17 parts of an anion-active Dispersant (formaldehyde, condensed with naphthalenesulfonic acid Sodium) and 125 parts of urea as a hydrotropic agent in 230 parts of water and 50 Parts of monopropylene glycol slowly added with vigorous stirring and for about 1 hour homogenized and deaerated. This approx. 53% agitation is then carried out in a closed Agitator ball mill (DYNO-MiIl type KDL) using silica-quartzite balls (1 mm diameter) for approx. 4 Milled hours. After this time a dispersion is obtained whose particle size is less than 3 microns is. By adding a further 50 parts of monopropylene glycol, 10 parts of 35% formalin solution and 18 Share a fatty alcohol polyglycol ether as a nonionic dispersant (etherified cetyl / stearyl alcohol with 25 mol of ethylene oxide) the millbase is diluted to 1000 parts and homogenized for 15 minutes. If necessary, a defoamer is also added. It is then separated from the grinding media, with a free-flowing, aqueous preparation with an active substance content of approx. 50 percent by weight receives. The preparation is low-viscosity (<100cP / 20 °). It is therefore advisable to grind in «0.75% Aerosil 200, the thin liquid dispersion easy to thixotropic (final viscosity 500 to 800cP / 20 °), whereby settling is prevented even after several months of storage.

If, instead of the stated optical brightener, the anionic dispersant, the nonionic dispersant and the hydrotropic agent, the same parts of the components given in Table II are used and the rest of the procedure as stated, storage-stable, free-flowing aqueous optical brightener dispersions with analogous properties are obtained whose active substance content and respective grinding time is determined by the texture of the crystalline brightener, the type of mill and the type of grinding media used and is between 40 and 60 percent by weight or 3 to 15 hours.

Table U

E.g. optical brightener
No.

21

22nd

H ₃ C

/ N ^ ^ N

| T C-CH = CH-C f!

VAo '^ o

CH ₃

CHj-N N-SO ₃ -

CH ₂

OH

23

CH = CH

/ N _n A

c ' ^N YY

VAo '

25 according to example 23

26 according to example J 21

27

28

^N \ Ij jl << ^N >

c-A Jl-C

according to example "2

B. Application of the preparations
Example 29

By stirring in a dye preparation prepared according to Examples 1 to 7 or 9 by means of vigorous Stirring in an aqueous polyacrylate solution gives printing inks. These inks can be used for paper can be printed using the rotary film printing process. The paper printed in this way can then be transferred using the transfer printing process, are preferably used in application to polyester textile materials, wherein sharply contoured, brightly colored prints are obtained.

Example 30

100 parts of the dye preparation according to Example 8 are dispersed in 1900 parts of water by stirring. The resulting liquor is used for impregnation Fabric made of mercerized cotton, squeezes to a weight increase of 60% and dries in the Hot air flow,

The tissue is then in an aqueous solution containing 20 parts of sodium hydroxide per liter and 40 parts of Natfiümdifhioriit at a temperature νοη 20 °, impregnated, reduced to 60% weight gain.

Anion-active Non-ionic Hydro tropes Dispersants Dispersants middle Sulfanated sulfone Fatty alcohol polyglycol urea getniscb from phenol and ether (stearyl / oleyl Naphthalene, partially ■ alkuhol etherified condenses with with 80 mol AeO) formaldehyde Condensation product the same the same from approx. 2 mol naphthalene sulfonic acid and I MoI formaldehyde

the same

the same

N-methylacetamide

Lignin sulfonate Hydroabietyl alcohol
etherified with 25 moles
Ethylene oxide Dimethyl
urea Lignin sulfonate Phenol ether (p-Nnnyl-
phenol etherifies with
9 moles of ethylene oxide) urea Lignin sulfonate Fatty alcohol poly-
glycol ether (oleyl
alcohol etherifies with
80 moles of ethylene oxide) Acetamide Condensation product
of formaldehyde with
Naphthalenesulfonic acid c Felt alcohol poly
glycol ether (cetyl /
Stearyl alcohol
etherified with 25 MoI
Ethylene oxide Dimethyl
urea Mixture of 1 part
Condensation product
from raw krcsol,
Formaldehyde and
Naphlhalinsulfonic acid with
I part of lignin sulfonate Hydroabietyl alcohol
etherified with
25 moles of ethylene oxide NM ethyl
acetamide

squeezes, steamed in an air-free steamer for 30 seconds and by oxidizing, rinsing, soaps and Drying completed in the usual way

The result is a strong, true yellow dyeing of excellent levelness.

Example 31

100 parts of the preparation according to Example 3 are with 1900 parts of diluted water. A polyester knitted fabric is impregnated with the dispersion obtained, squeezed off to 50% weight gain, dried in a stream of hot air and additionally for 60 seconds Heat-set at 200 ". The yellow dyeing obtained is rinsed and dried, which is reflected in a calm characterized by a smooth appearance and very good fastness properties,

Example 32

Dilute 100 parts of the dye preparation according to Examples 3 and 8 with 1800 parts of water, impregnates a mixed fabric of equal parts polyester and cotton in it, squeezes to 60% weight gain off, dries, heat-set for 60 seconds at 200 °, impregnated in an aqueous bath containing 20 parts of sodium hydroxide and 40 parts per liter

21

Sodium ditliionite, steams 60 seconds, oxidizes, rinses, soaps and dries. A level, yellow tone-on-tone dyeing of very good fastness properties is obtained calm product image.

example

A printing paste is produced by mixing 15 parts of a dye preparation according to Example 1 in 85 parts a 2.5% aqueous solution of a sodium alginate thickener be stirred in as a thickening of the stem.

This printing paste of approx. 800OcP is applied to paper with a gravure printing device printed paper can be transferred in the transfer process, e.g. B. on polyester textiles, use. It result sharp, level prints with high color depth.

It is noteworthy that the viscosity of the

Thickening of the trunk, the constancy of which is very important for a good pressure loss, by stirring in the high amount of dye is changed only very slightly.

Instead of the dye mentioned and the stem thickening mentioned, those of the following are used Table III used in the stated amount so that printing pastes are also obtained which either im ίο Flat film printing, rotary screen printing, gravure printing or in relief printing or in other suitable printing processes, such as spraying, spraying, brushing eto, can be used on paper or other suitable intermediate carriers.

Table III

Example dye preparation stem thickening

40
41
42
43
44
45
46
47
48
49

15 parts according to example 2

15 parts according to example 3

15 parts according to example 4

15 parts according to example 5

15 parts according to example 6

15 parts according to Example 7

15 parts according to example 9

15 parts according to example 1

15 parts according to example 2

15 parts according to example 3

15 parts according to example 4

15 parts according to example 5

15 parts according to example 6

15 parts according to Example 7

15 parts according to example 9

15 parts of example 1

85 parts of 2.5% strength aqueous solution of weakly alkaline, anionic Kernel meal derivative

85 parts of 2% strength aqueous solution of neutral, nonionic, depolymerized Guar flour

85 parts of 2% strength aqueous solution of neutral, nonionic hydroxyethylated Locust bean gum

85 parts of an oil-in-water emulsion with 1.5% gum ether

85 parts of 8% strength aqueous solution of nonionic, neutral corn flour ether thickening

85 parts of 2.5% strength aqueous solution of anionic, alkaline flour ether thickening

85 parts?, 5% aqueous solution of a mixture of nuclear methyl ether and Starch ether

85 parts of 5% strength aqueous solution of anionic weakly alkaline sulphate ether

85 parts of 2% strength aqueous solution of carboxymethyl cellulose

85 parts of 1.25% strength aqueous solution of hydroxyethyl cellulose

85 parts of 0.8% strength aqueous solution of a high polymer polyacrylic acid

85 parts of 6% strength aqueous solution of self-locking, thickening Acrylate-based polymer paste

85 parts of 6% strength aqueous solution of a dough from copolymer maleic acid based

85 parts of 6% strength aqueous solution of gum meal ether with colloidal silica

85 parts of 10% strength aqueous solution of ligninous carboxymethyl cellulose

85 parts of a water-in-oil-emulsion with Nä-Algiriat as a protective colloid

• ι
I,

Example 50

The printing pastes obtained according to Examples 33 to 49 can be based on textile materials printed from polyester, cellulose triacetate, polyamide or polyacrylonitrile and dried and according to can be fixed using the usual methods on the individual fibers. If desired, you can use these printing pastes further additives can be added for better fixation.

Example 51

It is possible to use the printing pastes obtained according to Examples 33 to 49 in order to achieve this in particular desired effects, such as levelness, dye yield or running properties, to be mixed with one another, provided the thickeners in question allow this.

Example 52

100 parts of the dye preparation according to Example 8 are diluted with 150 parts of water and dissolved in 750 Parts of a thickening consisting of 60 parts of a 10% strength aqueous starch ether solution, 10 parts of glycerol. 17 parts of potash, 4 parts of water and 9 parts of sodium sulfoxylate, stirred in.

The printing ink obtained in this way is applied to a cotton fabric of 120 g / m * weight in the normal way was pretreated for printing, printed using stencils, dried and then for 10 minutes steamed with exclusion of air at 100 to 105 "and then washed out. The result is a sharp, strong color print.

Example 53

The following preparation is provided: 30 parts of a locust bean gum derivative is mixed with 420 parts of water and stirred with a solution of 500 parts of water and 50 parts of starch ether High-boiling white spirit was added under the high-speed stirrer and a fabric made of cellulose viscose with a basis weight of 250 g / m ^{2 was printed using gravure rollers and dried} 880 parts of water, impregnated with 100% weight gain, pressed off and fixed in an air-free steamer at 120 ° for 35 seconds, then rinsed with cold and hot and dried. The result is a strong, sharp print with a yellow shade.

Example 54

150 parts of the dye preparation according to the example! 8 are incorporated into 850 parts of a solution dispersion of thermoplastic bodies and applied to a coated paper in the gravure printing process. After drying and, if necessary, storage, the paper is under pressure for 2 to 10 seconds at 200 ° with a normally pretreated cotton fabric of 120 g / m ² Basis weight brought into contact The transferred dye is now fixed and finished analogously to the fixation in Example 53 using an NaOH-Na-dithionite solution. The result is a strong, level print of yellow color, exactly reproducing the engraving units

24
Example 55

100 parts of the dye preparation according to Example 8 are stirred into 900 parts of the preparation described below and applied to a textile structure, which can consist of natural, regenerated or fully synthetic fibers, by any printing process. After drying, it is treated in hot air for 5 to 10 minutes at 140 to 150 ° ίο. A print of deep nuance is obtained. The preparation is made up as follows:
40 parts of water,

10 parts of condensed alkyl polyglycol ether and 30 parts of a 3% strength aqueous corn meal ether solution were mixed, subsequently

690 parts heavy gasoline (boiling range 120 to 180 °) incorporated into the express driver, then

.: - on-:

uigbii nauiigcil

phat solution and finally
200 parts of a 40% synthetic resin dispersion based on a self-crosslinking copolymer based on acrylate were added.

Example 56

50 parts of the dye preparation according to Examples 12 or J '·. are stirred into 950 parts of water. 7 parts of sodium acetate are added and a cotton fabric is padded in this dispersion. It is squeezed to 70% liquid absorption, dried on a cylinder dryer at 110 °. developed by padding in an aqueous bath with 30 g / l sodium hydrosulfite and 60 g / l 10N sodium hydroxide solution, steams for 60 seconds, rinses, oxidizes, washes, soaps and dries the dye. The result is a flat, calm blue coloration on both sides. Similar good results are also obtained with the 2-phase printing process.

Example 57

3 parts of a whitening agent formulation prepared according to Example 21 are converted into approx. 30,000 parts Water containing 30 parts of a fixing accelerator (nonionic Oxäthylierungsprodukt) introduced

1000 parts of a polyester staple fabric are in the resulting liquor (liquor ratio 1:30) in one Dyeing machine that allows temperatures above 100 °, treated as follows:

The temperature of the liquor increases within 30 minutes

120 ° driven. For another 30 minutes this will be

Tissue treated further at 120 ° and the liquor ran cooled to 70 ° within 10 minutes. The polyester fabric is rinsed with cold water and dried

The fabric treated in this way has an increase in whiteness compared to an untreated fabric 150 units of the CIBA-GEIGY white scale (see: CIBA-GEIGY Rundschau 1973/1, pages 10 to 25) on.

Example 58

4 parts of a whitening agent formulation prepared according to Example 23 and 1 part of a commercially available one Wetting agent is stirred into 1000 parts of water. A piece is made with the padding liquor obtained in this way Polyester pile fabric padded in such a way that the liquor pick-up is 70% of the goods weight treated polyester piece is dried at 80 ° for 10 minutes and then in a thermo

Fixing device thermoset for 30 seconds at 200 °. It is opposite to an air-treated fabric an increase in whiteness of 160 units of the GIBA-GEIGV whiteness scale.

Example 59

2 parts of a whitening agent formulation prepared according to Example 22 are stirred into 30,000 parts of water containing 30 parts of a fixing accelerator (non-organic oxethylation product) and -45 parts of 85% formic acid. 1000 parts of a polyacrylonitrile staple fabric are treated in the application liquor obtained at pH 3.5 (liquor ratio 1:30) according to the following temperature profile: The temperature of the liquor is increased to 97 ° over the course of 30 minutes. The tissue is further treated at this temperature for a further 30 minutes and then cooled to 70 within 10 minutes. The fabric is rinsed with cold water and dried.

The fabric treated in this way shows an increase in whiteness compared to the untreated fabric 120 units of the CLBA-GEIGY white scale.

Example 60

3 parts of a whitening agent formulation prepared according to Example 22 are dissolved in 30,000 parts of water, containing 90 parts of a commercially available reducing bleach, e.g. sodium dithionate, stirred in. 1000 Parts of a polyamide 66 woven tricot are added to the application liquor thus obtained (liquor ratio 1:30) treated according to the following temperature profile: The temperature of the liquor is within 30 minutes increased to 97 °. The tricot is treated at 97 ° for a further 30 minutes and then within Cooled to 70 ° for 10 minutes. The piece of woven tricot is rinsed cold and dried

The woven tricot treated in this way has an increase in whiteness of 140 units of the CIBA-GEIGY white scale.

Example 61

1500 parts of a copolymer containing 95% acrylonitrile and Contains 5% 2-vinylpyridine and has an average molecular weight of 47,000, are in 5500 parts Ethylene carbonate dissolved and the resulting solution filtered and deaerated. A Mixture of 2500 parts of ethylene carbonate and approx. 1000 Parts of water, in which 1 part of a whitening agent dispersion formulated according to Example 27 beforehand and 7.5 parts of oxalic acid have been added and homogenized, stirred in. The resulting spinning solution is then heated to 70 ° and at a rate of 200 g / min 7 nozzle through spinnerets with 412 holes (0.0076 cm diameter) in one

Pressed precipitation bath, which contains a mixture of 75% water and 25% ethylene carbonate. The bath temperature is kept at 60 °, while the freshly formed fibrils through the bath to a length of 122 cm be pulled through. The coagulated cable will run out

the bath at a speed of 9.3 m / min, pulled off and over two positively driven Rolls, which are arranged outside the bath and run at 9.4 m / min, or 44.5 m / min, so that the cable is stretched 4.8 times in the air. The cable is then passed through a stretch bath drawn, which contains water and 1 to 3% accumulated ethylene carbonate at a temperature of 100 °. The spinning rope is carried through the bath for a distance of 63.5 cm pulled, whereby an additional stretch of 1.64 times is achieved, so that a total stretch 7.7 times is achieved. The cable is then relaxed for a distance of 63.5 cm passed through a bath consisting essentially of water at 90 °. The resulting relaxed wet cable is squeezed off at a speed of 66 m / min, cut to the desired pile length, enriched and finally dried. In this way with 0.33% o active substance of the optical brightener from Example 8 lightened in the spinning mass

In contrast to the heavily yellowed untreated fiber, staple fiber is pure white.

Example 62

A printing paste for rotary film printing on paper is prepared by adding 0.5 to 1 part of one of the Examples 20 or 21 formulated optical brightener with about 9 parts of water and pre-diluted into 90 parts a stem thickening (6% aqueous solution of a dough made from a copolymer based on maleic acid) be stirred in. This printing paste of approx. 8000 cP is with a rotary film printing machine in a desired pattern applied to paper. The dried paper printed in this way can be transferred using the transfer process on polyester textiles (transfer printing at approx. 210 ° for 30 seconds). That on the paper The printed pattern is after the transfer on the polyester textile material due to its pure white effect visible. The pattern is particularly effective in rooms that are illuminated by UV radiation.

Claims (11)

Patent claims: 1. Finely dispersed, flowable preparations, consisting of water, insoluble to sparingly soluble in water Dyes or optical brighteners, the particle size of which is smaller than 10 μ, an anion-active and a nonionic dispersant, a hydrotropic agent and, if necessary, conventional ones Additions, characterized in that these preparations are at least 10 percent by weight Water, at least 30 percent by weight of a finely dispersed water-insoluble to sparingly soluble Dye or optical brightener and a mixture consisting of 0.1 to 5 percent by weight an anion-active dispersant, with the exception of the dispersants used in FR-PS 21 98 983, 1 to 3 percent by weight of a nonionic dispersant and 5 to 20 percent by weight of a hydrotropic agent. 2. Preparations according to claim i, characterized in that that this 35 to 65 percent by weight, preferably 40 to 60 percent by weight of dye or optical brighteners included. 3. Preparations according to claims 1 and 2, characterized in that they are used as in water insoluble to sparingly soluble dyes, base dyes for disperse dyes or vat dyes contain. 4. Preparations according to claim 1 and 2, characterized in that they are basic dyes for disperse dyes contain, which at atmospheric pressure between 150 and 220 ° C to at least 60% vaporize in less than 60 seconds. J5 5. Preparations according to claims 1 to 4, characterized in that they are anion-active Dispersants Condensation products of aromatic sulfonic acids with formaldehyde, lignosulfonates or contain polyphosphates. 6 preparations according to claims 1 to 4. characterized in that they are non-ionic Dispersing millel fatty alcohol polyglycol ether. Phenolic ethers or contain rinoleic acid. 7 preparations according to claims I to 4. 4> characterized in that they contain urea or dimethyl urea as hydrotropic agents. 8. Process / ur production of the aqueous preparations according to claims I to 7. thereby characterized in that the dye or ', < > Oplischen brightener in water with the addition of at least one of the said dispersants / p-grinds and the remaining components before. adds during or after the grinding process. 9. Use of the aqueous preparations according to y of claims 1 to 7 for coloring or printing or optical brightening of textile materials. Use of the optical brightener preparations according to Claims 1, 2 and ¹ to 7 in the aqueous drawing process on polyester, polyamide, polyacrylonitrile, cellulose acetate and cellulose acetate materials or in the aqueous thermal padding process on polyslermatfiridlien, or. 11. Use of the preparations according to claim 4 for transfer printing. Commercial forms of water-insoluble to sparingly soluble dyes or optical brighteners are known both as liquid brands and as powder brands. The latter have the disadvantage that they are before the applica toric use must first be dispersed in water; the former have the disadvantage that they have large amounts of dispersant, usually over 30 percent by weight, and little dye of the order of magnitude of about 20 percent by weight or optical brighteners of about 5 to 25 percent by weight. There was therefore a need, in particular for the preparation of printing pastes for printing on Carrier materials and their use in transfer printing are a commercial form for dyes that direct is usable and on the one hand a relatively small content of dispersant and on the other hand a has a high dye content, and which leads to, ··. * !! low in electrolytes should be to the use of electrolyte-sensitive too To make thickeners for the preparation of printing pastes more universal. It was just. aqueous preparations of in water insoluble to sparingly soluble dyes or optical brighteners found that the indicated Do not have disadvantages. These new aqueous preparations are low in dispersants, low in electrolytes, stable, highly concentrated in the definition of dye or optical brightener, finely dispersed, flowable and contain water-insoluble to sparingly soluble dyes or optical brighteners, their particle size is smaller than 10 μ, in particular smaller than 2 μ. These Preparations contain not less than 10 percent by weight and especially 20 to 30 percent by weight Water, at least 30 percent by weight, in particular 35 to 65 percent by weight, preferably 40 to 60 Percentage by weight of a finely dispersed water-insoluble to sparingly soluble dye or optical Brightener and a mixture consisting of 0.1 to 5 percent by weight of an anion-active dispersant. I to 3 percent by weight of a nonionic dispersant and 5 to 20 percent by weight of one hydrotropic agent and optionally other additives. The subject matter of the invention is therefore the preparations according to claims I to 7. their preparation according to claim 8 and their use according to the Claims 9 to 11. The basic dyes for the dispersers are the main dyes that are insoluble to sparingly soluble in water Sion dyes into consideration. From a chemical point of view, m different classes of dyes, such as. B. to nitro dyes. Aminoketor dyes. Ketone imine dyes, methine dyes. Nitrodiphenylanine dyes. Quinoline dyes, aminonaphthoquinone dyes. Coumarin dyes and in particular anthraquinone dyes and azo dyes, such as monoazo and disazo dyes. Vat dyes are also suitable. Typical representatives include B. following chemical Classes of: indigoid dyes; Anthraquinone dyes, including the anthrimides, anthraquinone endons, Anthraquinone thiazoles and anthraquinonyl azines and finally derivatives of fused ring systems; Nepheliphatic dyes; Pefylene * dyes; sulphurized carbazoles and quinori dyes. It should be noted that the type of dye within this given definition is largely determined by the Field of application of these aqueous dye preparations according to the invention. Are these "e.g. for preparation