CA1076304A - Aqueous preparations of dyestuffs or optical brighteners insoluble to difficulty soluble in water - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Described are aqueous, stable, highly concentrated, finely dispersed, flowable preparations of dyestuffs and optical brighteners insoluble to difficulty soluble in water, which preparations have a low content of dispersing agent and a particle size smaller than 10 µ, particularly smaller than 2 µ, characterized in that these preparations contain at least 10 per cent by weight of water, at least 30 per cent by weight of a finely dispersed dyestuff or optical brightener insoluble to difficulty soluble in water, and a mixture consisting of at most 10 per cent by weight of an anion-active dispersing agent, at most 5 per cent by weight of a nonionic dispersing agent and at most 35 per cent by weight of a hydrotropic agent, as well as, optionally, further additives which preparations are useful for the dyeing, printing and optical brightening of textile material in a conventional manner or for the production of printing pastes having an aqueous base or a water-in-oil-emulsion base which printing postes are useful for the printing of carrier materials, particularly paper with application of dyestuffs or optical brighteners suitable for transfer printing and use of the printed carrier materials in the transfer printing process on textile materials.

Description

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The invention relates to aqueous preparations of dyestuffs or optical brighte~ers insoluble to difficultly soluble in water, to processes for the production of these preparations~ to the use thereof for the preparation of aqueous printing pastes, as well as to the use of these for the printing of carrier materials and to their use in transfer printing, and also to the use of these preparations for the dyeing or optical brightening of textile materials, and to the printed carrier materials as well as to the textile material printed or optically brightened by means of these preparations in the transfer printing process, or dyed, printed or optically brightened by means of these preparations in the dyeing or prin~ing process.

Commercial forms of dyestuffs or optical brighteners insoluble to difficultly soluble in water are kno~n both as liquid preparations and as powder preparations. The latter have the disadvantage that they have to be firstly dispersed in water before application; the former have the disadvantage that they re~uire large am~unts of dispersing agent, in most cases over 30 per cent by weighL, and contain very little dyestuff, of the order of about 20 per cent by weight, or very little optical

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brightener, of the order of about 5 to 25 per cent by weight. There was therefore a need, particularly with regard to the production of printing pastes for printing of carrier materials and to the use of these S in transfer printing, to produce a commercial form of, in pa-ticular, dyestuffs which is directly ready ``
for use, and which contains on the one hand a relatively small amount of dispersing agent and on the other hand a large amount of dyestuff; and which, furthermore, has a lo~ electrolyte content, in order to thus render possible a more general application, for the preparation of printi.ng pastes, also of thickening ag.ents that are sensitive to electrolytes.

Aque~us preparations of dyestuffs or optical brighteners insoluble to difficultly soluble in water have now been found which do not have the disadvantages mentioneu. These new aqueous preparations have a low content of dispersing agents and of electrolytes, but a high CGIcentration of dyestuff ur optical brightener as defined, are stable, finely dispersed a~d flowable, and contain dyestuffs insoluble .o difficultly soluble in water, especially disperse dyestuffs or vat dyestuffs, or optical brighteners insoluble to difficultly soluble ;

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in water, of which th~ particle size is smaller than lO~u, particularly smaller than 2 ~. These preparations are characterised in that they preferably conta~n not less than 10 per cent by weight, especially 20 to 30 per cent by weight, of water, at least 30 per cent by weight, especially 35 to 65 per cent by weight, preferably 40 to 60 per cent by weight, of a finely dispersed dyestuff or optical brightener insoluble to difficultly soluble in water, and a mixture consisting of at most 10 per cent by weight, especially 0.1 to 5 per cent by weight, of an anion-active dispersing agent9 at most 5 per cent by weight, especially 1 to 3 per cent by weight, of a nonionic dispersing agent and a~
most 35 per cent by weight, particularly 5 to 20 per cent by weight, of a hydrotropic agent, optionally together with further additives.

Suitable dyestuffs insoluble to difficultly soluble in water ~re, in particular, disperse dyestuffs. Mention may be made, for e~ample, of the foundation dyestuffs of Celliton ~ and Palanil ~ dyestuffs of BASF, of Cibacet ~ and Terasil ~ dyestuffs of Ciba-Geigy, of Artisil ~ and Foron ~ dyestuffs of Sandoz, and of Duranol ~ dyestuffs of ICI, to mention just a few.

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Various chemical classes of dyestuffs are applicable, such as nitro dyestuffs, amino-ketone dyestuffs, ketoneimine dyestuffs, methine dyestuffs, nitro-diphenylamine dyestuffs, quinoline dyestuffs, amino- ~:
naphthoquinone dyestuffs, coumarin dyestuffs and, in particular, anthraquinone dyestuffs and azo dyestuffs, such as monoazo and disazo dyestuffs.

Further suitable dyestuffs are vat dyestuffs.
Typical representatives belong, for example, to the following chemical classes: indigoid dyestuffs;
anthraquinone vat dyestuffs, including also the anthrimide dyestuffs, anthraquinoneacridone dyestuffs, anthraquinone-thiazole dyestuffs as well as anthraquinonylazine dyestuffs and, finally, derivatives of condensed ring lS systems; naphthalene dyestuffs; perylene dyestuffs;
sulphurised carbazoles and quinone dyestuffs.

It is understood that the type of dyestuff within this given definition is to a great extent governed by the field of application for which these aqueous dyestuff preparations according to the invention are intended. If they are to be employed, for example, for the produ~tion of printing pastes and subsequent use in transfer printing, then the employed dyestuffs .
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insoluble to difficultly soluble in water will be those, within the limits of the given definitiong which are suitable for the transfer printing process, especially disperse dyestuffs which are converted at atmospheric pressure, at between 150 and 220~C, to the extent of at least 60% in less than 60 seconds into the vapour state, ~hich are stable to heat and which can be transferred undecomposed.
Such disperse dyestuffs are, for example, the monoazo dyestuffs of the formula OH
N - N -~O-Y X

wherein X and Y each represent an alkyl radical having 1 to 4 carbon atoms, OH
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N = N - C
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N02 '~'ÇO-CH3 _N = N - CH
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and, in particular, the quinophthalone dyestuff of the formula ~01~ 0 OH
- and the anthraquinone dyestuffs of the formulae , O NH-æ

O 'NH-Z
(Z c alkyl having 1 to 4 carbon atoms), ~3~ ~

~ ~R = alkyl or aryl) (R = Hal) O OH

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O ~H2 (~ ~ 1 r O NI~2 (Rl = allcyl having 3 to 4 carbon atoms), O N~ICH

O NH
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~ NH
~2 crl O NH-A
(A - alkyl or aryl), as well as brominated or chlorinated l,5-diamino-4,8-dihydroxyanthraquinones.
Also suitable however are reactive disperse dyestuffs that can be used in the transfer printing process, such . ~ , . .

~ ~ 7 6 3 0 4 as the dyestuffs of the formulae Cl-CH2-CO-NH ~--N = N ~

. H3 and c~3 0 N ~ N = N ~ N'C2H5 2 ~C2H40-CO CH2 Cl A further important factor is the choice of dyestuffs S in the case of dyestuff combinations, for only those dyestuffs that are similar in their transfer charactPristics should be combined in the transfer 2rinting process.

Suitable optical brighteners insoluble to difficultly soluble in water are, in particular, the following classes of compounds wi.h their nonionic substitution products:

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a) pyrazolines such as, for example, 1-(4-sulphamoyl-phenyl)-3-(4-chlorophenyl)-pyrazoline or 1-(4-methylsulphonylphenyl)-3-(4~chlorophenyl)-pyrazoline;
b) coumarins such as ~-phenyl-7-(3-methylpyrazol-1-yl)-S coumarin, 3-phenyl~7-(3-phenyl-4-methyl-1,2,3-triazoL-2-yl)-coumarin or 3-(4-chloro-1,2-pyrazol-1-yl)-7~(3-phenyl-4-mPthyl-1,2,3-triazol-2-yl)-coumarin;
c) mono~ and bis-benzoxazoles such as naphthaline-1,4-bis-benzoxazoie-(2), thiophene-2,5-bis-benæoxazole-(2), ethylene-1,2-bis-(5-methylbenzoxazole)-(2~, 2-(4-cyanostyryl)-596-dimethylbenzoxazole, 4-(597-dimethyl-benzoxazol-2-yl)-4'-phenylstilbene;
d) benzimidazoles such as uran-2~5-bis-(N-methyl-benzimidazole)-(2);
e) aryltriazoles such as 2-(4-chloro-2'-cyano-stilben-4'-yl)-naphtho-(1'~2':4,5)-1,2,3-triazole;
f) naphthoxazoles such as 2-(~ styryl)-naphtho-(1,2-d)-oxazole;
g) pyrenes such as 2-pyrenyl-4,6-dimethoxy-1,395-triazine;

h) naphthalimides such as 4-me~hoxy-N-methylnaph~halimide or 4,5-diethoxy-N-methylnaphthalimide;

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~ ~7~ 3 i) bis-ethylelle-aryls such as 1,4-bis-(2-cyanostyryl~
ben~ene, 4,4'-bis-(2-methoxystyryl-~)-biphenyl.

Furthermore, it is possible to use in the aqueous brightener prepara~îons also mixtur~s of different types of optical brighteners within the limits as defined.

Suitable anion-active dispersing agents are, e.g.:
sulphated primary or secondary, purely aliphatic alcohols of which the alkyl chain contains 8 to 18 carbon atoms, e.g. sodium lauryl sulphate, potassium-a-methyl stearyl sulphate, sodium tridecyl sulphate, sodium oleyl sulphate, potassium stearyl sulphate, or the sodium salts of coconut oil alcohol sulphates; sulphated, unsaturated higher fatty acids or fatty acid esters, such a~ oleic acid, elaidic acid or ricinoleic acid, or lower alkyl esters thereof, e.g. ethyl es~er, propyl ester or butyl ester, and the oils containing such fatty acids, such as olive oil, castor oil or rape oil; addition products of 1 to 20 moles of ethylene oxide with fatty amines, fatty acids or aliphatic alcohols having 8 to 20 carbon atoms in the alkyl chain, which addition products are converted into an acid ester by means of an organic dicarboxylic acid such as maleic acid, malonic acid or succinic acid, preferably however with an inorganic polybasic acid such as o-phosphoric acid or, ,. : . , .
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in particu. ar, sul.phuric a~.;.d, for example s-lch a~dition products with stearylamir.e, oieyl~nine, stearic acid, oleic acid, lauryl alcohol, myristyl alcohol, stearyl alcohol or oleyl alcohol, such as the ammonium salt of S sulphated lauryl alcohol triglycol ether, or of 1 to 5 moles of ~ hylene oxide with alkylphenols, such as the acid sulphuric acid ester of the addition product of 2 moles of ethylene oxide with 1 mole of p-nonylphenol, the acid sulphuric acid ester o~ the addition product of 1.5 moles of ethylene oxide with 1 mole of p-tert.oc~yl-phenol, the acid sulphuric acid ester of the addition product of 5 moles of ethylene oxide with 1 mole o~
p-nonylphenol, the acid phosphoric acid ester of the addition product of 2 moles of ethylene oxide with 1 mole of p-nonylphenol, the acid maleic acid ester of the addition product of 2 moles of ethylene oxide with 1 mole of p-nonylphenol; sulphated esterified polyoxy compounds, for example sulphated, partially esterified polyvalent alcohols, such as the sodium salt of the sulphated mono-2~ ~lyceride of palmitic acid; instead of sulphates, it isalso possible to use esters with o.her polyvalent mineral acids, e.g~ phosphates; primary and secondary alkyl-sulphonates of which the alkyl chain contains 8 to 20 : ', ;. .. ' ' ,~:' .
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carbon 2~0ms, e.g. ammonium decylsulphonate, sodium dodecylsulphorlate~ sodium hexadecanesulphonate and sodium stearylsulphonate; alkylarylsulphonates, such as alkyl-benzenesu'lphonate having a straight-chain or branched-chain alkyl chain containing at least 7 carbon atoms, e.gO
3 odium doi'ecylbenzellesulphonate, 1,3,5,7-tetramethyl-octylbenzenesulphonate, sodi~ octadecylb~nzenesulphonate;
such as alkylnaphthalenesulphonates, ~or example, sodium-l-isopropylnaphthalene-2-sulphonate; sodium dibuty'l-naphthalenesulphonate; or such as dinaphthylmethane-sulphonates', for example the disodium salt of di-(6-sulpho.aphthyl-2)-methane; sulphonates of polycarboxylic acid esters, for example sodium dioctyl sulphosuccinate, sodium dihexylsulphophthalate; the sodium, potassium, ammonium, N-alkyl-, N-hydroxyalkyl-, N-alkoxyalkyl- or N-cyclohexylammonium or hydrazinium and morpholinium salts of fatty acids having 10 to 20 carbon atoms, which are designated as soaps~ such as lauric, palmitic, stearic acid, or oleic acid of na~hthenic acids, of resinic acids, such as abietic acidj e.g. the so-called rosin soap; es~ers of polyalcohols, p~rticularly mono- or ~iglycerides of fatty acids having 12 to 18 carbon atoms, e.g. the monoglycerides of lauric 9 stearic, palmitic or ,. ' ' , ' ; . . ' ' ' ` . : 1 :. ::
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oleic acid, as well as the fatty acid esters of sugar aleohols, sueh as sorbitol, sorbitans and saccharose, for example sorbitan monolaurate (Span 20), sorbitan palmitate (Span 40), sorbitan stearate (Span 60), sorbitan oleat~ (Span 80), sorbitan sesquiolate, sorbitan ~rioleate (~pan 85), and the hydroxye~hyla~ion products thereof (~een).

Al~ion-active dispersing agents which have proved particularly favourable are condensation products of aromatic sulphonic acids with formaldehyde, such as eondensation products from formaldehyde and naphthalene sulphonie aeids, or from formaldehyde~ naphthalene-sulphonic acid and benzenesulphonic acid, or a condensation product from crude cresol, formaldehyde and naphthalene-sulphonic aeid, and lignin sulphorates and polyphosphates.It is also possible to Pmploy mixtures of anionic dispersing agents, such as, e.g., a mixture of the eondensat on product from erude eresol, formaldehyde and naphthalenesulphonic acid with lignin sulphonate.

Normally, the anionic disperslng agents are in the form of their alkali salts, their ammonium salts or their water-soluble amine salts. It is advantageous to use qualities having a low eontent of foreign electrolytes.

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Nonionic dispersing agen~s are, for example:
addition products of, e..g., 5 to 50 moles of alkylene oxides 5 especia].ly ethylene oxide (with some ethylene oxide units being able to be replaced by substituted epoxides such as styrene oxide and/or propylene oxide), with high_r fatty acids, or with saturated or unsaturated alcohols, mercaptans or amines having 8 to 20 carbon atoms, or with alkylphenols or alkylthiophenols of which the alkyl radicals contain at least 7 carbon atoms;
reaction products from higher-molecular fatty acids and hydroxyalkylamines; these can be prepared, for example, ~rom higher-molecular fatty acids, preferably such ones having about 8 to ~0 carbon atom~, e.g.
caprylic ~cid, stearic acid, oleic acid and, in particular, lS from the mixture of acids embraced by the collective term "coconut oil fatty acid", and from hydroxyalkyl-amines such as triethanolamine or preferably diethanol-amine, as well as from mixtures of these amines, with the reaction ~eing so performed that the molecular quantity ratio between hydroxyalkylamine and fatty acid is greater than 1, for example 2:1. Such con~?ounds are described in the American Patent ~pecification No. 2,089,212;
condensation products of alkylene oxide, especially ... . . . .
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ethylene oxide, with some ethylene oxide units being able to be replaced by substituted epoxides, such as styrene oxide and/or propylene o~ide.

Fatty alcohol polyglycol ethers have proved particularly advantageous, especially those having more than 20 moles of ethylene oxide, such as cetyl-stearyl alcohol etherified with 25 moles of ethylene oxide, stearyl-oleyl alcohol etheri~ied with 80 moles of ethylene oxide and oleyl alcohol etherified with 20 to 80 moles ~f ethylene oxide. Furthermore, phenol ethers such as p-nonylphenol etherified with 9 moles of ethylene oxide, ricinoleic acid ester having lS moles of ethylene oxide and hydroabietyl alcohol etherified with ~5 moles of ethylene oxide are also very suitable.

Thesæ nonionic dispersing agents advantageously have a low electrolyte content. Mixtures of such agents are possible and in some cases have synergetic effects.

By hydrotropic agents used in the aqueous preparations according to the invention are meant those agents ca~able of converting the dispersion of the dyestuffs or optical bri~hteners insoluble to difficultly soluble in water into a stable deflocculated form, without :: ,., : ..

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in the process a chemical reaction occurring between the dyestuff or the optical brightener and the hydrotropic substance. These compounds should be water-soluble. Suitable substances having these properties are, for example: hydrotropic salts such as the sodium salt of benzoic acid, the sodium salt of benzene-sulphonic acid, the sodium salt of p-toluenesulphonic acid or the sodium salt of N-benzylsulphanilic acid.
Compounds which have proved particularly advantageous in this connectiolt are, however, ritrogen-containing compounds, such as urea and derivatives thereof, for example dimethylurea or guanidine chloride, or acid amides such as acetamide and propionamide and derivatives thereof, especially N-methylacetamideO

With the application accordi.g to the invention of the hydrotropic substance in combination with dispersions of the dyestuffs or optical brighteners as defined, a stabilisa~ion of the deflocculated dispersion is obtained without any actual dissolving of the dyestuffs or optical brighteners occurring.

By virtue of this combination according to the invention, namely of the anion-active and nonionic dispersinO agent together with the hydrotropic agent . _ _ - ; , . . . :

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in the given amounts, it is possible to obtain aqueous preparations which have on the one hand a low c~ntent of dispersing agent and, on the other hand, a high content~of dyestuff or of optical brightener, and which are characterised in particular by their stability both in the hot state and in the cold state in a temperature range of between about minus 10C and plus 60C; by a storage-stability of several months;
by free flowability; by their finely dispersed form;
and by their low viscosity in the range of about 10 to lO00 c~/20C.

In cons`equence of the high propor~ion by weight of dyestuff or optical brightener, the aqueous preparations according to the invention are very compact and provide a saving in space. A reduction of the space required for storage and dispatch and in transport is therefore ensured.

If desired or required, these preparations can contain further additives for improving properties, such as hygroscopic agents, e.g. glycols or sorbitols;
antifrost agents, e.g. ethylene glycol or monopropylene glycol; antimicrobics; fungicides, e.g. aqueous formalin solution; antifoaming agents and agents improving ~ . . . . . .... .. . ...

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viscosity .
As a result of the presence of about 10% of sorbitol, there can moreover be obtained a fully satis~actory redispersibility of the completely dried-out paste.
It is obvious that in the case of brightener preparations there are used only such anionic and nonionic dispersing agents and hydrotropic agents which have no noticeably disadvantageous effects on the fluorescence of the brighteners (e.g. so-called quenching ~ffects). Furthermore, on subsequent applicaticn in 'Foulardtherm' (hot padding) processes, these auxiliaries must be able to withstand the short exposure to heat at 150 to 220C without yellowing.
By virtue of their high content of dyestuff or optical brightener, these preparations are greatly superior to the liquid preparations hitherto available commercially~ since, on account of their smailer content of dispersing agents and extenders~ they can be processed into low-viscous printing inks having an adequate concentration of dyestuff or of oD~ical brightener. In the printing on paper using solvent-free, purely aqueous printing processes, by means of roller-printing, Flexo-: - . ... . .
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printing and, in particular, rotary-screen-printing machines, highly concentrated preparation systems having a low content of dispersing agents are required. since paper, compared with textile materials, has a clearly reduced absorption capacity for printing inks, the recipes suitable for direct printing on ~extiles, especially in the case o deep shades, camlot be used.

The new aqueous preparations are produced, for example, by a process in which the dyestuff or optical brightener as defined is mixed and ground in water with at least one of the mentioned anion-active and/or nonionic dispersing agents, an operation which is carried out, e.g., in a ball mill or sand mill, with the remaining constituents being added before, during or even after the grinding process, so that a preparation having a particle size smaller than 10 Ju, especially smaller than 2 ~, is obtained.

The new aqueous dyestuff preparations can be used, advantageously after dilution with water, for the dyeing 2Q or printin~ of textile materials by the continuous or discontinuous method of operation. Depending on the dyestufs used in the preparations, the widest variety o textile materials can be dyed or printed therewith, .. ....
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such as polyester or cellulose triacetate materials or mixtures of fibres by application of preparations containing disperse dyestuf~s.

In the preparation also of printing pastes for S traditional textile printing, it is of advantage to employ preparations having the lowest possible content of d~spersing agent, since the disperse dyestuffs at present available contain large amounts of dispersing agent~ wh-ch have to be washed ou~ after fixing o~
the dyestuff and thus unnecessarily contaminate the waste water.

Since the preparations according to the present invention have an electrolyte content that is low compared with that of commercial preparations of disperse dyestuffs, the thickeners used for the production of the said printing pastes can be sensitive to - elPctrolytes. In this connection, thickeners in particular having a polyacrylic base have proved especially valuable.

A preferred possibility of application is moreover that these dyestuff preparations ran be used, with the employment of thickeners~ for the production of printing pastes having an aqueous base or a water-in-oil-emulsion base, which printing pastes are used for the printing of . . . : ~ , ;
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carrier materials which, in their turn, can be used in the transfer printing process on textile materials~
The carrier materials that are printed with such printing pastes are known, and consist advantageously of a flexible sheet material that is preferably dim.ensionally stable, such as a strip, band or sheet, preferably having a smooth surface. These carrier materials must be stable to heat, and they are made of the most varied types of materials, particularly non-textile materials, such as metal, e.g. an aluminium or steel sheet; or they consist of a continuous strip o~ stainless steel, plastics or paper, preferably of a clean, non-lacquered cellulose parchment paper, which is optio~ally coated with a film of vinyl resin, ethyl-cellulose, polyurethane resin or Teflon.~
me optionally ~iltered printing pastes or printing inks are applied to the carrier material, in places or over the whole surface, by, for example, spraying, coating or, advantageously, printing. There can also be applied to the ~rrier material a multicoloured pattern, or the carrier material can be printed with a ground shade and thereafter successively with identical or ~Trademark for a tetra~luoroethylene fluorocarbon resin.

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different d~si~ns. After application of the printing paste to the carrier material? this is dried~ e.g.
with the aid of a warm flow of air or by infra-red irradiation.
S The carrier materials can be printed also on both sides, whereby it is possible to select different colours and/pr designs for the two sides~ In order to avoid the use of a pr;nting machine, the printing pastes can be sprayed onto the ca~-rier materials by means of, for example, a spray gun. Particularly interestlng effects are obtained when simultaneously more than one shade is printed or sprayed on the carrier material. Specific designs can be obtained, e.g., by the use of stencils, or artistic designs can be applied by brush. If the carrier m2teri~ is printed, then the most diverse printing processes may be employed, such as high-pressure processes (e.g. letter-press printing, flexographic printing), gravure printing (e.g. roller printing), screen printing (e.g. rotary printing or film printing) or electrostatic yrinting processes.
The transfer is effected in the usual ma~ner by the action of heat. For this purpose, the treated carrier materials are brought into contact with the materials - 23 ~

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to be printed, especially textile materials, and are held at about 120 to 210C until the defined dyestuffs applied to the carrier material have been transferred to the textile material. As 2 rule, 5 to 60 seconds S are sufficient to achieve this.

The action of heat can be applied by various known methods, for example by passage over a hot heating cylinder, by passage through a tunnel-shaped heating zone, or by means of a heated roller, advantageously together with a pressure-exerting, heated or unheated counter roller, or by means of a hot calender, or with the`aid of a heated plate, optionally under vacuum, which devices are preheated to the required temperature -by steam, oil, infra-red irradiation or microwaves, lS or which are located in a preheated heating chamber.

After completion of the heat treatmen~, the printed material is separated from the carrier. The material requires no aftertreatment~ neither a steam treatment to fix the dyestuff, nor a washing to improve the fastness properties.

The new aqueous optical brightener preparations are used, preferably and advantageously after dilution - 2~ - ;;

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with water, for ~he optical brightening of textile materials by, e~g., the exhaust process, high-temperature exhaust process and 'Forlardtherm' process.
Further suitable dispersing agents or other auxiliaries can optionally be added for stabilisation of the liquor and/or or obtainment of carrier effects.

The widest variety of textile materials are suitable such as polyester materials, polyamide, polyacrylo-nitrile, cellulose acetate and cellulose triacetate, and these materials can be in the most diverse stages of processing. It is moreover possible for these preparations to be used for the production of printing pastes, which are employed either for conventional brightening of, in particular 9 textile materials, or for printing of carrier materials, such as especially paper, which in their turn are used in the transfer printing process on textile materials.

A further application for the optical brigh~ener preparations according to the invention is, finally, in spinning-solution brightening.
The following examples illustrate the invention without limiting ;ts scope to them. IPar~s' denote parts by ~eight, and temperatur~s are given in degrees Centigrade.

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A Production of ~he preparations .

Example 1 500 par~s of the coarse crystalline dry dyestuff of the formula ~ .~' O OH

are slowly introduced, with intensive stirring (Dissolver or Lodig2-Mischer (mixers)), into a pre~prepared solution of 25 parts of an anion-active dispersing agent (sodium salt of naphthalene sulphonic acid condensed with formaldehyde), 10 parts of a fatty alcohol polyglycol ether as nonionic dispersing agent (cetyl/stearyl alcohol etherified with 25 moles of ethylene oxide), 10 parts of a 35% aqueous formalin solution, 100 parts of 1,2-propylene glycol as antifrost agent and 118 parts of urea, as hydrotropic stabilising agent, and the whole is lS then homogenised for about 1 hour and deaerated.

This 55% dyestuff mixture is ~hen ground in a sand ;;
mill, or preferably in a closed ball mill (bead mill), by means of Ottawa sand and Siliquarzit balls (1 mm diameter), respectively, for about 10 hours at a temper-ature of 20 to 50. After this time there is obtained a .. . , . ... . . .... , . . . . . ... ... . :: ... .. . .

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dispersion of which an overwhelming majority of particles are smaller than 5 ~. The finely ground dispersion is subsequently diluted to give a dyestuff content of 50% (yield: 1000 parts) by the addition of a further ~Q parts of water, which if necessary contains an amount (to be determined beforehand) of carboxymethyl-cellulose as thickening agent, in order to bring the final viscosity into the ideal range of 500 to 1000 cP
~Brookfield viscosimeter; 30 r.p.m.).

The free-flowing aqueous preparation remains completely unchanged even throughout a storage time of several months, and withstands without impairment temperatures of -15 to +40.

`If, instead of the dyestuff, the anion-active dispersing agent, the nonionic dispersing agent and the hydrotropic agent given in the above example, there are used identical parts of the constituents shown in the following Table I, with otherwise the same procedure, then likewise there are obtained storage-stable, free-flowing, aqueous dyestuff preparations having analogousproperties, of whieh the dyestuff content and respective grinding time are governed by the dyestuff concerned, and are between 40 and 60 per cent by weight and 5 to 10 hours, respectively. - 27 -- 1 . . , .. . ..
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~ ~ 7 ~ 3 Example 12 500 parts of the dried and pulverised press cake of dichloro-indanthrone are stirred into a solution of 130 parts of urea, 10 parts of sodium dinaphthylmethane sulphonate, 20 parts of a condensation product of stearyl/cetyl alcohol with 25 moles of ethylene oxide, in 100 parts of monopropylene glycol and 240 parts of water, and the whole is ground, with the addition of 2000 part~ of glass balls of 1 mm diameter, until the particle size is essentially about 1 to 2 microns. The preparation is then separated from the balls.
There is obtained a free-flowing, s~orage-stable dyestuff preparation.

~xample 13 S00 parts of the crude dyestuff of the formula N~ ~N~ ~ N

~C' '~ .

- : . - -- ... . ........
., ;, ~ ~ 7 ~ 3~ ~

are ground together with a solution of lO parts of a condensation product of naphthalenesulphonic acid and formaldehyde, 20 parts of the reaction product of p-nonylphenol and 9 moles of ethylene oxide, 130 parts S of urea, lO0 parts of ethylene glycol and 370 parts o water with 2000 parts of sand until the particle size is around 1 to 2 microns, and the sand is then removed.
There is obtained a pourable stable dyestuff preparation.

Example 1~
480 parts of the coarse crystalline dry dyestuff of the fo~mula ~ ' H "

are slowly introduced, with intensive stirring (Dissol.ver 1$ or Lodigc~Mischer (mixers)), into a pre-prepared solution of 24 parts of an anion-activz dispersing agent (sodium naphthalene sulphonate condensed with formaldehyde), lO parts of a fatty alcohol polyglycol ether as a nonionic dispersing agent (cetyl/stearyl alcohol etherified - 32 ~

~ . ' ~" '",,; " ~', ';, . ' , '~ .

~ 3 ~ ~

with 25 moles of ethylene oxide), 10 parts of 35%
aqueous formalin solution, 100 parts of 1,2~propylene glycol as an antifrost agent and 124 parts of urea, as a hydrotropic stabilising agent, in 172 parts of water, and the whole is homogenised for about 1 hour and deaerated.

The approx. 52% dyestuff mixture is then ground in a sand mill, or preferably in a closed ball mill, 91q55 1-~ by means of Ottawa sand and ~ {~ t~ bàlls (1 mm diameter), respectively, for about 10 hours at a temperature of 20 to 50. After this time there is obtained a dispersion of which the overwhelming majority of particles are smaller than 5 ,u. The finely ground dispersion is subsequently diluted to give a dyestuff content _f 48% (yield: lOOQ parts) by the addition of a further 80 parts of water which; if necessary, contains an amount (to be determined beforehand) of car~oxymethyl-cellulose as a thickening agent, in order to bring the final viscosity into the ideal range of 500 to 1000 cP
(Brookfield viscosimeter; 30 r.p.m.). The free-flowing aqueous preparation remains completely unchanged even after a storage time of several months, and withstands without impairment temperatures of -15 to -~40.

' ': ~ . ; ' ' :
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.
400 parts of the coarse crystalline dry dyestuff of the formula O ~H
~ ~ N

are slowly introduced, with intensive stirring (Dissolver or Lodige-Mischer tmixers]), into a pre-prepared solu~ion "
of 20 par~s of an anion-active dispersing agent (sodium naphthalene sulphonate ~ondensed with formaldehyde), 20 parts of a fatty alcohol polyglycol ether as a nonionic`dispersing agent (cetyl/stearyl alcohol etherified with 25 moles of ethylene oxide), 10 parts of 35% aqueous formalin solution, 100 parts of 192-propylene glycol as an antifrost agent and 150 parts of urea~ as a hydrotropic stabilising agent, in 190 parts of water, and the whole i~ then homogenised for about 1 hour and deaerated.
This 45% dyestuff mixture is subsequently ground in a sand mill, or preferably in a closed ball mill, by means of Otta~A7a sand and Siliquarzit balls (1 mm diameter), respectively, for about 10 hours at a temperature of 20 to 50. After this time there is obtained a dispersion .. , .. . ....... ~.~ .. .. ............. , ........ ,.. , . .. .. ..... .. " .. ~, ~ ~ 7 ~ 3~ ~

of which an overwhelming majority of particles are smaller than 5 ~. The finely ground dispersion is diluted to give a final dyestuff content of 40%
(-- 1000 parts) by the addition of a further 110 parts of water containing if necessary an amount (to be determined beforehand) of carboxymethylcellulose as a thickening a~ent, in order to bring the final viscosity into the ideal range of 500 to 1000 cP (Brookfield viscosi~eter; 30 r.p.m.). The free-flowing aqueous preparation remains completely un~hanged even ater a storage time of several months, and withstands without impairment temperatures of -15 to ~40.

Example 16 482 parts of the coarse crystalline dry dyestuf of the formula o NH-CH3 ~

are slow]y introduced, with intensive stirrîng (Dissolver or Lodige-Mischer [mixers]), intc a pre-prepared solution of 20 parts of an anion-active dispersing agent (sodium naphthalene sulphonate condensed with formaldehyde), 15 :- : .' ! ' :- ' . . . ' ':' ~' '. ' ' ' , . .
~'. ' . ' . :
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~763C~4 parts of a fatty alcohol polyglycol ether as a 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 an antifrost agent and 120 parts of urea, as a hydrotropic sta-bilising agent, in 145 parts of water~ and the whole is then homogenised for about 1 hour and deaerat~d.
This 54% dyestuff mixture is then ground in a sand mill, or preferably in a closed ball milI, by means of Ottawa s~nd and Siliquarzit balls (1 mm diameter), respectively, for about 10 hours at a temperature of 20 to 50. After this time there is obtained a dispersion of which the overwhelming majority of particles are smaller ,than 5 ~. The finely ground dispersion is diluted to give the fin~l dyestuff content of 48.2% by the addition of a further 108 parts of water containing if necessary an amount (to be determined beforehand) of carboxymethyl cellulose as a thickening agent, in order to thus bring the final viscosity into the ideal range of 500 to 1000 cP
~Brookfield viscosimeter; 30 r.p.m.). The ree-flowing aqueous preparation remains completely unchanged even after a storage time of several months, and withstands without impairment temperatures of -15 to ~40.

. _._.. ~ ._ .. _ .
~ .

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Example 17 150 parts of a yellow dispersion according to Example 14, ~50 parts o a red dispersion according to Example 1, S 300 parts of a blue dispersioll according to Example 15, and 200 parts of a blue dispersion according to Example 16 are homogenised in a stirring vessel.
There are obtained 1000 parts of a black formulation having a viscosity in the range of 500 to 1000 cP
(Brookfield viscosimeter; 30 r.p.m.).
The free-flowing. highly concentrated aqweous paste remains completely unchanged even after a storage time of several months, and withstands without impairment temperatures of -15 to ~40.

.. , .. . ... . , . . , .. ,, . . .. . . . ... .. , ... , ,.,~ ,, .. .- ., :
:: ; :, ,, , ~ . - ,,;

. ~ .
,: ::: . . -~ ~ 7 6 ~ 4 E~ample 18 ~:
445 parts of the coarse crystalline dry dyestuff of the formula O N~l ` Jl ~H- ~

are slowly introduced~ with thorough stirring (Dissolver or Lodige-Mischer [mixers~), into a pre-prepared solution of 10 parts of an anion-active dispersing agent (sodium naphthalene sulphonate condensed with formaldehyde), 20 parts of a fatty alcohol polyglycol ether as a 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 a~
antifrost agent and 137 parts of urea as a hydrotropic stabilising agent in 205 parts of water, and the whole is then homogenised for about 1 hour and deaerated.
lS This 48% dyestuff mixture is then ground in a sand mill, or preferably in a closed ball mill, by means of Ottawa sand or Siliquarzit balls ~1 mm diameter) for about 10 hours at a temperature of 20 to 50. There is obtained after this time a dispersion of which an - 3~ -.. . ~,,, , .. ,., , .. . .. . ...... . ._ .. :. .. ..
.:

. ,~ ... . ..
. . . :.: :

~ ~ 7 ~ 3~ ~

overwheming majorlty of particles are smaller than 5 ~. The finely ground dispersion is diluted to give a inal dyestuff content of 44.5% (= 1000 parts) by the ad~ition of a further 73 parts of water containing if necessary an amount (to be determined beforehand) of carboxymethylcellulose as a thickening agent, in order to thus bring the final viscosity into the ideal range o~ 500 to 1000 cP (Brookfield viscosimeter; 30 r.p.m.).
The free-flowing aqueous preparation remains completely unchanged even after a storage time of several months, and withstands without impairment temperatures of -15 to ~40.

: `: ' ' ' .. ' , ' '' ' ''., 1 ' ~;
~: . ' .: - , : . ' ' 1~763~

Example 19 415 parts of the coarse crystalline dry dyestuff of the formula o NH
f 3 O N~12 are slowly introduced, wi`th thorough stirring (Dissolver or Lodige-Mischer [mixers]), into a pre-prepared solution of 5 parts of an anion-active dispersing agent (sodium naphthalene sulpllonate condensed with formaldehyde), 20 parts of a fatty alcohol polyglycol e~her as a nonionic dispersing agent (cetyl/stearyl alcohol etherified with 25 moles of ethylene oxide), 10 par~:s of 35% aqueous formalin solution, 100 parts of 1,2-propylene glycol as an antifrost agent and 150 parts of urea as a hydrotropic stabilising agent in 222 parts of water, and the whole is homogenised for about 1 hour and deaerated.
This 45% dyestuff mixture is subsequently ground in a sand mill, or preferably in a closed ball mill~ by g I~S5 A means of Ottawa sand and SiliquarK~ balls (1 mm diameter), respectively, for about 10 hours at a temperature of 20 to 50. There is obtained after this time a dispersion of which an overwhelming majority of particles are smaller ' '`, , ,, , ,' , ~ . ' ', ' ' ,.,., ...,., ,,.,.. .. .'. " , ' . .. ., '....

.

~t763~

than 5 ~1. The finely ground dispersion is diluted to give a final dyestuff content of 41.5~/o (= 1000 parts) by the addition of a further 78 parts of water containing if necessary an amount (to be determined beforehand) of S carbox~nethylcellulose as a thickening agent, in order to thus bring the final viscosity into the ideal range of 500 to 1000 cP (Brookfield viscosimeter; 30 r.p.m.).
The free flowing aqueous preparation remains completely unchanged even after a storage time of several months, and withstands without impairment temperatures of -15 to ~40.

:;:... , , .: , .. ..

~ ~ ~ 6 3~ ~

~3~
500 parts of the pure dry active substance of the optical`brightener of the formula ` ~ ~c ~Lc~

are slowly introduced, with vigorous stirring, into a solution of 17 parts of an anion active dispersing agent (ormaldehyde condensed with sodiUm naphthalene sulphonate~ and 125 parts of urea, as the hydro~ropic agent, in 230 par~s of water and 50 parts of monopropylene glycol, and the whole is homogenised for about one hour and deaerated. This approx. 53% mixture is then ground in a closed ball mill (DYN0 mill, ~ype KDL) by means of Siliquarzit balls (1 mm diameter) for about 4 hours. After this length of time there is obtal~ed a dispersion having a particle size of less than 3 ~l. The ground material is diluted to 1000 parts by the addition of a further 50 parts of monopropylene glycol, 10 parts of 35% aqueous formalin solution, as well as 18 parts of a .: . :: ,.
:
: '' '' : " ' ~ 3~ ~

fatty alcohol polyglycol ether as a nonionic dispersing agent (cetyl-stearyl alcohol etherified with ~5 moles of ethylene oxide), and the whole is then homogenised for 15 minutes. There is optionally also added an anti-foaming agent. The grinding agent is subsequently removed t~ leave a free-flowing aqueous preparation having a content of active substance of about 50 per cent by weight. This preparation ~las a low viscosity ( ~100 cP/20C). It is therefore advisable to render the thinly liquid dispersion slightly thixotropic by grinding in ~ 0.75% of Aerosil 200 (Degussa) [final viscosity 500-S00 cP/20C~, as a result of which a settling out, even after a storage time of several months, is to a great extent avoided.

If, instead of the optical brightener, anion-active dispersing agent, nonionic dispersing agent and hydrotropic agent given in the above example, there are used identical parts of the constituents shown in the following Table II, with the procedure being otherwise as described, then likewise there are obtained storage-stabLe, free-flowing aqueous o~tical brightener dispersions having analogous properties, of which the active-substance content and , ~;, , 97~3~ 4 grinding ~ime are in each case governed by the ~extureof the crystalline brightener, by the type of mill and by the nature of ~he gr;nding agents used, and are between 40 and 60 per cent by weight and 3 to 15 hours, respectively.

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~7di3~4 B. A?plication of_the prepar~t-iolls Printing pastes are obtained by the mixing, by vigorous stirring~, of a dyestuff preparation produced according to Examples 1 to 7 or 9 into an aqueous polyacrylate solution. These printing pastes can be used for printing paper in the rotary screen printing process. The paper thus prin~ed can then be used in the transfer printing process, preferably ~ith applicatic~a to poiyester textile materials, with sharply outlined, deeply coloured printings being obtained.

Example 30 `
100 parts of the dyestuff preparation according to Example 8 are disp2rsed by stirring in 1900 parts of water.
A fabric made from mercerised cotton is impregnated with the liquor thus obtained; the material is squeezed out to lS leave an increase in weight of 60%, and subsequen~ly dried in a stream of hot air.
The fabric is afterwards impregnated in an aqueous solution containing per litre 20 parts of sodium hydroxide and 40 parts of sodium dithionite at a temperature of 20C, and the material is then squeezed ollt to give a 60%

increase in weight; it is subsequen~ly st~med in a steamer ` - 47 -.. -:: . ': .
. .. .
: .. ., . -:, . .
.. .. . .
: . . .
,- . . .

~L~G7~

fl~e rrom air for 30 seconds, and is ~hen finished by oxida~ion, rinsing, soaping and drying in the usual manner.
There is obtained a strong, fast yellow dyeing S having ~xcellent levelness.

Example 31 100 parts of the preparation accord;ng to Example 3 are diluted with 1900 parts of watPr. A polyester fabric is impreg~ated with the resulting dispersion and then squeezed out to 50% increase in weight; it is dried in a stream ~ hot air, and additionally thermofixed for 60 seconds at 200. The yellow dyeing obtained is rinsed and dried, the resulting dyeing is characterised by a solid level appearance and very good fastness properties.

Example 32 In each case, 100 parts of the dyestuff preparation according LO Examples 3 and 8 are diluted with 1800 parts of water; there is then impregnate~ therein a mixed fabric made from identical parts of polyester and cotton;
the material is squeezed out to 60~/o increase in weigh~, dried and thermofixed for 60 seconds at 200; it is subsequently impregnated in an aqueous bath containing : ' ;.: , ' ~ , , .
. . :- :,, , ;, ~763~

per litre 20 parts of sodium hydroxide and 40 parts o sodium dithionite, then steamed ~or 60 seconds, oxidised, rinsed, soapPd and dried. There is obtained a level yellow ~one-in-tone dyeing having very good fastness properties and a solid appearance.

Example 33 A printing paste is prepared by stirring lS parts of a dyestuff preparation according to Example l into 85 parts o- a 2.5% aqueous solution of a sodium alginate thickeni-ng as the stock thickening.
This printing paste of about 8000 cP is applied with a photogravure printing device ~o paper~ The paper thus printed can be used in thb transfer printing process, e;g. on polyester textiles. There are ob~ained sharply outlined ievel prints having a high intensity of colour.
It is -~orthy of note that the viscosity of the stock thickening, the consistency o which is very important for a good 2rinting result, is only very slightly changed by the stirring-in of the large amount of dyest-lf.
If, i~qtead of the stated dyestuff and the stock thickening mentioned, those given in the following Table III are used in the amount given, then likewise ' .1 . . '' ', ` ~ ., ' ' " ~'" ' " ' ; ' ' ' ' ' , . . ' , , ' ' ' , , ', ' ' : ~ ~
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, . ........ . .
' . ;. ,' ', ',',. ' 1~76~(~4 there are obtained printing pas~ which can be used on paper OL on other suitable intermedi.ate carriers in flat screen printing, in rotary screen printing, in photogravure printing or in relief printing, or in other suitable pril~ting processesg such as spraying, brushing, etc..

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Example 50 The printing pastes ob,a-nPd according to Examples 33 to 49 can be printed on textile materials based on polyester, cellulose triacetate, polyamide or polyacrylonitri]e, and subsequently dried and fixed by methods nornally applied for the individual fibres. Further ~dditives may optionally be added to these printing pastes to impro~e fixing.

Example 51 It is possible, provided that the thickening agents concerned permit it, to mix together the printing pastes obtained according to Examples 33 to 49 in order to obtain specifically desired effec~s~ such as levelness, dyestuff yi~ld or run properties.

Example 52 100 parts of the dyestuff preparation according to Example 8 are dilwted with 150 parts of water, and the whole is stirred into 750 parts of a thickening consisting of 60 parts of a lOV/o aqueous starch ether solution, 10 parts o~ glycerin, 17 par.s of potassium carbonate, 4 parts of water and 9 parts of sodium sulphoxylate.
The printing paste thus obtained is printed by means of stencils on a cotton fabric of 120 g¦m2 in weight, which has been pre~r~ated in the normal manner for printing, ~63763~

dried, ~nd afterwards steamed for 10 minutes at 100-105 with the exclusion of air and subsequently washed.
There is obtained a sharply outlined~ de~ply coloured print.

Example 53 -The following preparation is produced:- 30 parts of a locust bean flour derivative are mixed with 420 parts of water, and the whole is stirred together with a solution of 500 parts of water and 50 parts of a starch ether. To 7 parts of this preparation there are added, under a high-speed stirrer, 1 part of the dyestuff prcparation according to Example 8, 1 part of water and 1 part of a high-boiling spirit, and the whole is then printed, by means of heliogravure rollers, onto a fabric made from cellulose-viscose having a weight per unit are of 250 g/m2, and subsequently dried. The material is afterwards impregnated wi~h an aqueou3 solution containing 40 parts of ~aOH, 65 parts of Na-dithionite, 15 parts of borax and 880 parts of water; it is then squeezed out to lOQ% increase in weight and fixed in a steamer free from air for 35 seconds at 120; it is finally rinsed cold and then hot and dried. There is obtained a strong, sharply outlined print in a yellow shade.

.' ~ ' ' ' . ' ,' ', ',^ 1-' - ' ' ' ' ' ' ' ', -' 7' ` ~ ' ' ` : ' _ , ., ._ ., . _. _ _____. __ _ _~ _ ,', . .. " ., ' ' '',, ' , " . ', '' ,, ', , ' ~ ~ ' ,, ' " ' '"',' ',''f ' ' ~ ~ 6 3 Example 54 150 par~s of the dyestuff preparation according to Example 8 are worked into 850 parts of a solution-dispersion of thermGplastic substances, and the whole is applied to a coated paper in the heliogravure process. Af~er drying and, optionally, storage, the paper is brought into contact under pressure for 2 to 10 seconds at 200 with a cotton fabric having a weight per unit area of 120 g/m2, which has been normally pretreated for printing. The transferred dyestuff is afterwards fixed analogously to the fixing in Example 53 by means of an NaOH-Na-dithionite solution and finally finished. The result is a strong level yellow printing exactly reproducing the fine de~ails of the engraving.

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Example 55 100 parts of the dyestuff preparation according LO
Example 8 are stirred into 900 parts of the preparation describèd below, and the whole is applied by any desired printing process to a textlle article which can be S made from natural, regenerated or fully synthetic fibres. After drying, the material is treated in hot air for 5 to 10 minutes at 140 to 150. There is obtained a printing in a deep shade.
The said preparation is obtained as follows:
40 parts of water, 10 parts of condensed alkylpolyglycol ether and 30 parts of a 3% aqueous carob bean flour ether solution are mixed together; subsequently, 690 parts of heavy b~næene ~boiling range 120 to 180) are worked in with a high-speed stirrer, then 30 parts of a 30% aqueous diammonium phosphate solution and, finally, 200 parts of a 40/ synthetic resin dispersion based on autocross-linking copolymers having an acrylate base are added.

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~7~i3~ -50 parts of the dyestuff preparation according to Examples 12 or 13 are stirred in~o 950 parts of water.
There are also added 7 parts of sodium acetate, and a cotton fabric is then pad dyed in this dispersion. The material is squeezed out ~o 70% liquid absorption; it is dried on a cylinder drying machine at 110 and developed by padding in an aqueous bath containing per litre 30 g of sodium hydrosulphite and 60 g of lON sodium hydroxide solution; the dyeing is subsequently steamed for 60 seconds, rinsed, oxidised, washed, soaped and dried.
There is obtained a solid bLue dyeing level on the surfaces and sides. Similarly good results are obtained also by the 2-phase printing process.

Example c-3 parts of a brightener formulation produced ~5 according to Example 21 are stirred into about 30,000 parts of water containing 30 parts of a fixing accelerator (nonionic oxyethylation product). 1000 parts of a polyester staple fabric (Dacron 54~ are treated in the following manner in the liquor ob~ained (ra~io of goods to liquor 1:30) in a dyeing apparatus that permits temperatures of over 100-~ irrQ~/e ~ Q~

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" , 1~763~4 The temperature of the liquor is raised within30 minutes to 120. The fabric is treated at 120 for a further 30 minutes, and the liquor is then cooled within 10 minutes to 70. The polyester fabric is S rinsed cold and dried.

Compared with an untr~ated fabric, the fabric treated in the manner described shows an increase in the degree of whitene,ss of 150 units of the CIB~-GEIGY
scale of whiteness (see: CIBA-GEIGY Rundschau 1973/1 pages 10 to 25).

Example 58 4 parts of a brightener formulation produced according to Example 23 and 1 part of a commercial wetting agent are stirred into 1000 parts of water.
A piece of polyester staple fabric (Dacron 54) is padded with the padding liquor ~hus obtained in such a manner that the liquor absorption is 70% of the weight of the goods. The polyester piece treated in this way is dried at 80 ~or 10 minutes, and subsequently thermofixed in a thermofixing apparatus for 30 seco~lds at 200. Compared with an untreated fabric, the treated fabric shows an increase in the degree of whiteness of 160 units of the CIBA-GEIGY scale of whiteness.

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763~

le 59 2 parts o~ a brightener formulation produced according to Example 22 are stirred into 30,000 parts of water containing 30 parts of a fixing accelerator (nonionic oxyethylation product) and r~45 parts of 85% formic acid. 1000 parts of a polyacrylonitrile staple fabric (Orlon 75) are treated in the resulting applica~ion liquor at pH 3.5 (ratio of goods to liquor 1:30) according to the following procedure: the temperature o the liquor is raised within 30 minutes to 97; the fabric is treated for a further 30 minutes at this temperature, and then cooled to 70 within 10 minutes. The fabric is rinsed cold and dried.

ComparPd with the untreated fabric, the fabric treated in the described manner ~h~ws an increase in the degree of whiteness of 120 units of the CIBA-GEIGY
scale of whiteness. ;

Example 60 3 parts of a brightener formulation produced according to Example 22 are stirred into 30,000 parts of water containing 90 parts of a commercial redwcing bleaching agent, e.g. sodium dithionite. 1000 parts of a polyamide 66 woven tricot are treated in the resulting , .. ..... , ~ .. .. .. .... .. ... , .. ... .. ,, .. ...... ; . , ~"",~, - . , : ~

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application liquor (ratio of goods to liquor 1:30) according to the following procedure: the temperature of the liquor is raised within 30 minutes to 97; the tricot is treated at 97 for a further 30 minutes and then cooled to 70 in the course of 10 minutes.
The woven tricot piece is rinsed cold and dried.
The wnven tricot treated in the described manner shows, compared with an untreated substrate, an i~crease in degree of whiteness of 140 units of the CIBA-GEIGY
scale of whiteness~

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~ 7 ~ 3 Example 61 1500 parts of a copolymer which contains 95% of acrylonitrile and 5% of 2-vinylpyridine and has a mean molecular weight of 47,000 are dissolved in 5500 parts of ethylene carbonate, and the solution obtained is filtered and deaerated. Into this solution there is s~irred a mixture of 2500 parts of ethylene carbohate and about 1000 parts of water, in which beforehand l part of a brightener dispersion formulated according to Rxample 27 and 7.5 parts of oxalic acid have been added and homogenised. The formed spinning solution is then heated to 70 and îs extruded, at a speed of 200 g/minOlnoz~le through spinning nozzles having 412 holes ~0.0076 cm di~meter), into a precipitating bath containing a mixture of 75~/O of water and 25% of ethylene carbonate. The bat'n r temperature is maintained at 60 while the freshly formed fi~rils are dra~. through the bath to a length of 122 cm.
The coagulated tow is drawn out of the bath at a speed of 9.3 m/min. and over two positively driven rollers which are arranged outside the bath and run at a speed of 9.3 mtmin. and 44.5 m/min., respectively, so that the tow is stretched in air to the extent of 4.8 times its former length. The tow is then drawn through a stretching .
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~763~4 bath containing water and 1 to 3% of accumulated ethylene c~rbonate at a temperature of 100. The tow is dra~n through the bath over a distance of 63.5 cm, as a result of which there is achievPd an additional 1.64-fold stretching, so that the overall stretching obtained is 7.7 times the original length.
The tension is released and the tow is subsequently passed, over a distance of 63.5 cm, through a bath consisting essent ally of water at 90. The resulting slack tow is squeezed out at a rate of 66 m/min., cut to the desired length of staple, finished and finally dried. In contras~ to Lhe severely yellowed untreated fibre, the staple fibre brightened in this manner wi~h 0.33 o/oo of active substance of the optical brightener from Example 8 is pure white.

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Example 62 A printing paste for rotary screen printing on paper is produced by pre-diluting 0.5 to 1 part of an optical brightener formulated according to Example 20 or 21 with about 9 parts of water, and stirring it into 90 parts of a stock thickening (6% aqueous solution of a paste made from a copolymer based on maleic acid).
This printing paste of abou~ 8000 cP is applied in a desired design to paper using a rotary screen printin~
machine. T.le dried paper printed in this manner can be used, in the transfer prin~ing process, on polyester ~ex~iles (transfer at approx. 210 during 30 seconds).
The design printed onto paper is visible after transfer to the polyester textile material by virtue of its pure white effect. The design is particularly effective in rooms illuminated by UV-radiation.

'~. , ' ,'

Claims (29)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Aqueous, stable, highly concentrated, finely dispersed, flowable preparations of dyestuffs and optical brighteners insoluble to difficultly soluble in water, which preparations have a low content of dispersing agent and a particle size smaller than 10 µ, characterised in that these prepara-tions contain at least 10 per cent by weight of water, at least 30 per cent by weight of a finely dispersed dyestuff or optical brightener insoluble to difficultly soluble in water, and a mixture consisting of an anion-active dispersing agent, in an amount of at most 10 per cent by weight, a nonionic dispersing agent in an amount of at most 5 per cent by weight and a hydro-tropic agent in an amount of at most 35 per cent by weight.

2. Preparations according to claim 1 which contain 0.1 to 5 per cent by weight of an anion-active dispersing agent, 1 to 3 per cent by weight of a nonionic dispersing agent and 5 to 20 per cent by weight of a hydrotropic agent.

3. Preparations according to claim 1 which contain 35 to 65 per cent by weight of dyestuffs or optical brighteners insoluble to difficultly soluble in water.

4. Preparations according to claim 1 which contain, as dyestuffs insoluble to difficultly soluble in water, disperse dyestuffs or vat dyestuffs.

5. Preparations according to claim 1 which contain, as dyestuffs insoluble to difficultly soluble in water, such dyestuffs that are suitable in the transfer printing process.

6. Preparations according to claim 5 which contain disperse dyestuffs that convert at atmospheric pressure, at between 150 and 220°C, to the extent of at least 60% in less than 60 seconds to the vapour state.

7. Preparations according to claim 1 which contain, as optical bright-eners insoluble to difficultly soluble in water, derivatives of pyrazolines, coumarins, mono- and bis-benzoxazoles, benzimidazoles, aryltriazoles, naph-thoxazoles, pyrenes, naphthalimides and bis-ethylene-aryls.

8. Preparations according to claim 1 which contain, as anion-active dispersing agents, condensation products of aromatic sulphonic acids with formaldehyde, lignin sulphonates or polyphosphates.

9. Preparations according to claim 1 which contain, as nonionic dis-persing agents, fatty alcohol polyglycol ether, phenol ether or ricinoleic acid ester.

10. Preparations according to claim 1 which contain, as hydrotropic agents, nitrogen-containing compounds.

11. Process for the production of the aqueous preparations according to claim 1, wherein the dyestuff or optical brightener as defined is ground in water with the addition of at least one of the dispersing agents mentioned, and the remaining components are added before, during or subsequent to the grinding process, so that there is thus obtained a preparation of which the particle size is smaller than 10 µ.

12. A method of dyeing, printing or optically brightening textile materials which comprises applying an aqueous preparation according to claim 1 to said textile material.

13. Method according to claim 12 for optically brightening polyester, polyamide, polyacrylonitrile, cellulose acetate and cellulose triacetate materials which comprises applying the aqueous optical brightener preparation of claim 1 during the aqueous exhaust process.

14. Method according to claim 12 for optically brightening polyester materials which comprises applying the aqueous optical brightener preparation of claim 1 during the aqueous 'Foulardtherm' process (hot padding process).

15. A method for the production of printing pastes having an aqueous base or a water-in-oil-emulsion base which comprises adding the aqueous preparation of claim 1 to a printing paste thickener.

16. The printing pastes obtained according to claim 15.

17. Printing pastes according to claim 16 which contain thickeners having a polyacrylic base.

18. A method for the printing of a carrier material by the application of a printing paste which comprises a dyestuff or optical brightener suitable for transfer printing according to the preparation of claim 1.

19. Preparations according to claim 1 having a particle size smaller than 2 µ.

20. Preparations according to claim 1 containing 40 to 50 per cent by weight of said dyestuffs or optical brightener.

21. Preparations according to claim 10 wherein said nitrogen-containing compound is urea or dimethylurea.

22. Method according to claim 18 wherein said carrier material is paper.

23. Preparation according to claim 1 containing 40 to 60 per cent by weight of the dyestuff of the formula 0.1 to 5 per cent by weight of an anion-active condensation product of naphthalenesulphonic acid with formaldehyde (Na salt), 1 to 3 per cent by weight of cetyl-stearyl alcohol, etherified with 25 moles of ethylene oxide, 0.5 to 2 per cent by weight of 35% aqueous Formalin solution, 8 to 12 per cent by weight of 1,2-propylene glycol, 5 to 20 per cent by weight of urea, and 20 to 30 per cent by weight of water.

24. Preparation according to claim 1 containing 40 to 60 per cent by weight of the dyestuff of the formula 0.1 to 5 per cent by weight of an anion-active condensation product of naphthalenesulphonic acid with formaldehyde (Na-salt), 1 to 3 per cent by weight of cetyl-stearyl alcohol, etherified with 25 moles of ethylene oxide, 0.5 to 2 per cent by weight of 35% aqueous Formalin solution, 8 to 12 per cent by weight of 1,2-propylene glycol, 5 to 20 per cent by weight of urea, and 20 to 30 per cent by weight of water.

25. Preparation according to claim 1 containing 35 to 65 per cent by eight of the dyestuff of the formula 0.1 to 5 per cent by weight of an anion-active condensation product of naphthalenesulphonic acid with formaldehyde (Na-salt), 1 to 3 per cent by weight of cetyl-stearyl alcohol, etherified with 25 moles of ethylene oxide, 0.5 to 2 per cent by weight of 35% aqueous Formalin solution, 8 to 12 per cent by weight of 1,2-propylene glycol, 5 to 20 per cent by weight of urea, and more than 10 per cent by weight of water.

26. Preparation according to claim 1 containing 40 to 60 per cent by weight of the dyestuff of the formula 0.1 to 5 per cent by weight of an anion-active condensation product of naphthalenesulphonic acid with formaldehyde (Na-salt), 1 to 3 per cent by weight of cetyl-stearyl alcohol, etherified with 25 moles of ethylene oxide, 0.5 to 2 per cent by weight of 35% aqueous Formalin solution, 8 to 12 per cent by weight of 1,2-propylene glycol, 5 to 20 per cent by weight of urea, and 20 to 30 per cent by weight of water.

27. Preparation according to claim 1 containing 40 to 60 per cent by weight of a dyestuff mixture of the dyestuffs of the formulae ' and 0.1 to 5 per cent by weight of an anion-active condensation product of naphthalenesulphonic acid with formaldehyde (Na-salt), 1 to 3 per cent by weight of cetyl-stearyl alcohol, etherified with 25 moles of ethylene oxide, 8 to 12 per cent by weight of 1,2-propylene glycol, 0.5 to 2 per cent by weight of 35% aqueous Formalin solution, 5 to 20 per cent by weight of urea, and 20 to 30 per cent by weight of water.

28. Preparation according to claim 1 containing 40 to 60 per cent by weight of the dyestuff of the formula 0.1 to 5 per cent by weight of an anion-active condensation product of naphthalenesulphonic acid with formaldehyde (Na-salt), 1 to 3 per cent by weight of cetyl-stearyl alcohol, etherified with 25 moles of ethylene oxide, 0.5 to 2 per cent by weight of 35% aqueous Formalin solution, 8 to 12 per cent by weight of 1,2-propylene glycol, 5 to 20 per cent by weight of urea, 0.2 per cent by weight of an antifoaming agent, and 20 to 30 per cent by weight of water.

29. Preparation according to claim 1 containing 35 to 65 per cent by weight of the dyestuff of the formula 0.1 to 5 per cent by weight of an anion-active condensation product of naphthalenesulphonic acid with formaldehyde (Na-salt), 1 to 3 per cent by weight of cetyl-stearyl alcohol, etherified with 25 moles of ethylene oxide, 0.5 to 2 per cent by weight of 35% aqueous Formalin solution, 8 to 12 per cent by weight of 1,2-propylene glycol, 5 to 20 per cent by weight of urea, 0.1 per cent by weight of an antifoaming agent, and more than 10 per cent by weight of water.