DE2850808A1 - MELT TRANSFER PRINTING - Google Patents

Description

51 709-Dr. T

COMMONWEALTH SCIENTIFIC AND INDUSTRIAL RESEARCH ORGANIZATION Limestone Avenue, Campbell, Australia

Melt transfer printing

The invention relates to a method for inking, printing or decorating materials, in particular, but not exclusively, in the form of textile fabrics, using a melt transfer process.

It is known that colored patterns of substrates such. B. paper, by softening a transfer layer under the action of pressure and heat in a calender or in can be transferred to textiles in a press. Transfer papers, which contain water-soluble or water-dispersible dyes, according to the US patents 2 911 280, 3 589 962 and 4 027.34-5 by coating specially treated types of paper with one or more release layers before or after applying a print pattern. After the transfer of the pattern on the fabric, the dyes are applied by conventional methods that are appropriate for the types of tissue used and for the dyes used are fixed to the textile fibers. A serious disadvantage of this method is that it has multiple layers must be applied to the papers, since water-soluble or water-dispersible dyes are not included in the

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Separating layers can be incorporated. A single The printing process would allow the transfer papers to be made much easier and cheaper. A single Printing is possible when pigments are dispersed in water-insoluble thermoplastic materials and on release papers can be printed. In this case the thermoplastic materials function as both transmission media as well as a binder for the pigments. The pressure generated by transferring these papers onto a fabric however, feel very hard on the printed surfaces because of the presence of the thermoplastic material. Such prints are in no way similar to prints in which dyes are absorbed by the fibers or by diffusion are fixed in the fibers which build up the fabric, as is the case with the method according to the invention.

In British Patent 1 4-96 891 there is a related one Class of transfer printing preparations described in which the coloring materials (dyes) with a film-forming Polymers, especially a vinyl polymer, are combined. These preparations are in the form of a Layer applied or printed on a flexible substrate, for example on paper, which itself has a special Has coating to allow easy and complete transfer of the polymer film and its content to the printable Ensure material. The film does not melt, but rather retains its identity during the broadcast stage.

The one described in British Patent 1-496.891 Process has various disadvantages, in particular it is necessary to use a specially treated substrate material to use, and the fact that those used

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Vinyl polymers are thermoplastic polymers and therefore the same problems as discussed above can arise.

It is therefore an object of the present invention to provide a printer inks or to specify a paste preparation for use in melt transfer printing that enables coloring materials (dyes) and substances that build up the separating layer to mix with each other and in one Operation to be printed on the substrate, in which, however, those with the use of film-forming and thermoplastic Problems associated with polymers are avoided. Another object of the invention is to provide a method of melt transfer printing indicate in which the above preparations are used, with the help of which substrates with a Transfer layer can be coated or printed using conventional methods and with the same Help using conventional methods of coloring agents (dyes) on the items to be printed or decorated Materials can be transferred and fixed on it.

The invention generally relates to coloring or paste preparations, which are characterized in that they contain or consist of a mixture of

(i) a substance or a mixture of substances that functions as a melt transfer medium,

(ii) at least one colorant (dye) and (iii) water.

Depending on the circumstances described below, the

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Preparations according to the invention also contain one or more of the following ingredients:

(iv) one or more thickeners, depending on the Printing of the substrates used processes,

(v) means used to achieve color development or Fixation of certain dyes (dyes) are required,

(vi) printing auxiliaries to improve the quality of the prints on the substrate,

(vii) substances to increase the durability of the printed layer on the substrate and

(viii) Substances that are printed by transfer printing Give material special properties.

The main component of the earb or paste preparation according to the invention is the substance or the mixture of substances (i), which (that) under the influence of heat and / or pressure as Transfer medium for transferring the coloring material (dye) from the transfer substrate to the one to be printed Material works. The colorants (dyes) must be soluble or dispersible in the substrate and adhere firmly to the material to which the pattern is to be transferred under conditions of heat and / or pressure. One Another important requirement is that they should be soluble or dispersible in water, since water is the continuous phase of the printing paste forms and the water solubility or dispersibility in water the removal the transfer medium from the transfer printed material by washing it out with water after Fixing of the colorants (dyes) facilitated.

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For the purposes of the present invention, substances that meet these conditions are polymers derived from cyclic ethers, or mixtures of these polymers. The polymers are preferably ethylene oxide polymers of the general formula R (OOILjCHp) OR ', where η is the average number of oxyethylene groups per molecule and R and R ^{1 are} hydrogen or alkyl groups having 1 to 18 carbon atoms. Suitable polymers have an η with a value within the range from 10 to 100,000, but the most advantageous properties have polymers in which R and R ¹ denote hydrogen, methyl or ethyl groups and η has values from 300 to 3000 ..

Some suitable commercial products are Polyox WSRH-10, Polyoxyethylene glycol compound 2OM and Carbowax 20,000, the all made by Union Carbide Corporation, and P.E.G. HM100, P.E.G. ΛΗΜ6, P.E.G. HM50 and P.E.G .. AHM5, manufactured by Höchst.

All of these polymers are of the non-film-forming type and essentially have one waxy character. Unlike the film-forming polymers, which are used as transmission media in the known preparations become the preparations according to the invention soft or melt and flow from the substrate paper onto the material to be printed, whereby they have a slight Leave the amount of colorant (dye) and transfer medium on the substrate after the transfer step.

It is possible to use individual polymers with η values that are smaller and are greater than the above-mentioned preferred values for

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individual polymers to mix with each other and still good Obtain results provided that the average value for η thereby obtained is within the preferred Area. The polyoxyethylene polymers or polymer blends should be 5 to 40% by weight of the aqueous paint solution or make up printing paste, depending on the type of printing Materials. For many fabrics, good results have been obtained with concentrations within the range of 10-20 % By weight obtained.

Suitable colorants or dyestuffs (ii) for incorporation into the printing pastes are all water-soluble or in Water dispersible dyes. The amounts and types of these dyes depend on the desired shade and the The type of material to be decorated. Dyes with good solubility in the printing paste are best suited However, dyes with poor solubility can be obtained by grinding the paste in a ball mill or in a Roller mill to be dispersed. The classes of dyes for use as the coloring components of fabrics and film materials that can be used according to the method according to the invention are as follows:

Acid dyes, milled dyes, metal complex dyes, Chrome dyes, disperse dyes, fiber-reactive dyes, Direct dyes, basic dyes, azo dyes, developing dyes, oxidation dyes, sulfur dyes and vat dyes. Water-soluble or water-dispersible optical brighteners can also be used in the pastes be included either alone or in combination with colorants. The types of dyes and optical brighteners, which are suitable for the material to be colored,

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are those skilled in the art of dyeing and printing known per se. E-reserve or dye-aids can can be used in the printing paste together with the dyes or replace them to achieve differential Coloring effects. These effects can be achieved by removing the printed fabric after the Eeserve has been fixed. or excessively stains dyeing auxiliaries. The printing pastes can also be added together with dyes or instead of the same discharge agents to achieve a discharge and Achieve spark discharge effects on fabrics that are prior to Printing have been colored. The one for every type of textile fabric agents used and the methods of development these effects are known to those skilled in the art of dyeing and printing textiles. The amount of Dyes, optical brighteners, auxiliaries, resist agents or discharge means can be between 0.01 and 20 wt.%, based on the weight of the printing ink or printing paste, vary.

For the production of pastes that can be printed on substrates Using certain methods, it may be necessary to adjust the viscosity by adding thickeners to increase. Up to 10% by weight of synthetic or natural thickeners, such as starch gum, Alginates, starch ethers, carboxymethyl cellulose and polymers containing carboxylic acid groups can be used, them however, are in concentrated solutions of polyoxyethylene polymers not very effective. As the most effective method, thickening with white spirit is preferred. Therefore, 0.1 Up to 5% by weight of a suitable emulsifying agent of the printing paste can be added to emulsify from 5 to 55% by weight of white spirit in the aqueous phase to enable to achieve

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the desired increase in viscosity. Preferred formulations for printing paper with flat or rotary screens contain 0.5 "to 2.0% by weight of an emulsifying agent, such as, for example, Emulsifying Agent 3240 (Bayer) or Teric 16A29 (Imperial Chemical Industries Limited), and 20" to 4 -5 wt.% white spirit, which is a hydrocarbon oil fraction, at least 50 / boiling of the ° ° in. the boiling range of I50 to 250 ⁰ C.

An optimal color development and fixation of some dyes can only be achieved in the presence of suitable protective and fixing agents can be achieved and these can be the printing ink or printing paste in the required dimensions up to one Limit of 10% by weight, based on the entire preparation, can be added. The types of substances that are different for different Dyes are suitable are known to those skilled in the art of dyeing and printing and are included generally pH control agents, oxidizing or reducing agents, or metal salts. Preferred substances however, are those that are stable solids with low vapor pressures at room temperature. In the case of certain Dyes, e.g. B. some from the classes of fiber reactive dyes and azo dyes, is an attitude the pH value of the printing ink or printing paste is required to ensure its stability and its fixation to improve the transfer to the material to be printed. Preferred substances for this purpose are acids, Bases and salts and in particular sulphamic acid and its salts and the salts of formic acid, acetic acid, phosphoric acid and carbonic acid, with the sodium and potassium salts being particularly preferred. Certain dyes, such as B. some from the class of oxidation and fiber reactive dyes,

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require the presence of oxidizing or reducing Substances in the printing ink or printing paste that act as stabilizers or their fixation on the to improve the material to be printed. Preferred substances for this purpose are sodium chlorate, sodium nitrite, sodium bisulf it, sodium metabisulfite, sodium hydrosulfite and Sodium and zinc formaldehyde sulfoxylate. Metal salts play an important role in fixing some dyes, whereby they either act as catalysts for chemical reactions of the dyes, such as. B. with oxidation dyes, or act as mordants which prevent the formation of dye-met "Enable all-complexes, such as" for chromium dyes. Preferred catalysts are water-soluble salts of copper and vanadium, with copper sulfate and sodium and ammonium vanadate being particularly preferred. Suitable pickling agents are water-soluble salts of transition metals of the periodic table of the elements and especially chromium containing salts, of which chrome alum, chrome (III) fluoride and sodium and potassium dichromate are particularly preferred.

To improve the durability of the printed on the substrate Layer by improving its resistance to Blocking, smearing or rubbing, up to 20% by weight of substances can be added to the printing ink or printing paste will. Preferred substances are aqueous emulsions of acrylic, urethane, silicone or ethylene polymers. Samples of effective emulsions are Primal K3 and Primal HA2O (Primal Chemicals), Impranil DUST and Xmpranil DLH (Bayer), Dicrylan WK (Ciba Geigy) and Valsof PE34- (Valchem Pty. Ltd.). It is Surprisingly, it has been found that the amount of ink transferred during the melt transfer printing stage increases when these substances are contained in the printing paste.

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If necessary, agents which modify the performance of the printing ink or printing paste during the printing process and improve the quality of the print on the substrate can also be added up to a limit of 10% by weight, based on the weight of the preparation. Preferred substances are wetting agents and antifoam agents, such as Matexil WA-KB (ICI), Antimussol WL (Sandoz) and Etingal A (BASi ¹ ). If necessary, agents capable of imparting special properties to materials during or after melt transfer printing can also be contained in the printing ink or printing paste. Preferred substances are textile surface treatment agents which improve the color fastness, give setting, surface finish, flame retardant, moth fastness, waxing and shrinkage resistance effects. Up to 20% by weight of these substances can be added to the printing ink or printing paste.

The invention also relates to a printing medium for melt transfer printing, that contains or consists of a suitable substrate, which with a preparation according to the invention is coated or printed.

Suitable substrates consist of a flexible material with a flat surface that is preferably dimensionally stable remains little or under the conditions of the preliminary pressing and the melt transfer step deformed. Paper is the preferred material, but foils or films made of synthetic polymeric materials are also suitable, such as polyesters and polycarbonates, and metal foils. Paper is preferred as it is generally cheap is enough to be able to carry out a transfer

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pressure to be thrown away. In contrast, the known methods discussed above require specially treated ones and therefore more expensive release papers made with clay, silicon, polyethylene, polypropylene, acrylic polymers or blends of these substances, have been impregnated to ensure acceptable transfer of the coloring material (dye) to achieve. It has surprisingly been found that there are acceptable results in practicing the invention can be obtained using commercially available lithographic paper that does not have any special treatment has been subjected. However, the use of treated papers is not excluded according to the invention.

The printing ink or printing paste can be prepared using any conventional mechanical or manual method be applied to the transfer substrate in film form for coating, printing or otherwise decorating materials. Such procedures include the spraying on, the padding with a lick roller, that Application by means of a doctor blade and, in particular, printing. The most suitable procedures are those in which aqueous printing inks or printing pastes can be used, such as. B. rubber printing and screen printing. Screen printing process, in which flat or rotating screens are used are particularly suitable. On the printed

5 b of printing paste should be applied to the substrate.

Surface of the substrate should be 5 to 35 -g / m dry weight

The invention also provides a method for melt transfer printing, which comprises the following stages:

(1) Contact the material to be printed with a

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Substrate which is coated with an inventive printing ink or Printing paste preparation has been coated or printed,

(2) Transfer of the dried coating or print from the substrate to the material to be printed by transfer printing using heat and / or pressure,

(3) Completion of the fixation of the colorants (dyes) in the transferred onto the material to be printed Layer with the application of heat or by treatment with water vapor,

(4-) Washing the transfer printed material with water to remove soluble residue from the transfer layer and unfixed colorant (Dye).

Because of the special properties of the transfer layer, certain methods of performing the steps of the Method preferred. These procedures are detailed in the relevant sections below.

The method according to the invention is suitable for dyeing all types of knitted, woven and non-woven fabrics and sheet materials such as felts and films containing a component that is soluble in or in water dispersible dyes can be colored or printed and on which the dyes are fixed by heating and / or by treatment with steam. About suitable dyeable components for these fabrics or film materials include protein fibers such as those made from wool, mohair, rabbit hair, or silk; Cellulose fiber ^ like such

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made of cotton, viscose rayon, cellulose acetate and linen; Fibers made from synthetic polymers such as polyamides, polyalcohols, Polyvinyl derivatives, polyesters, polyacrylics, polyurethanes, Polypropylenes, polyethylenes; Leather; synthetic and natural rubber; and mixtures or composite materials, made from these materials.

The melt transfer stage should preferably be at a temperature of 30 to 150 ⁰ G and at a pressure of 1 to

2
200 kg / cm can be carried out. The contact between the transfer substrate and the material to which the print is to be transferred can be temporary or it can last up to 10 minutes, depending on the pressure and temperature and the required degree of penetration of the dye and the transfer medium into the print Material. Calenders consisting of two pressure rollers, one or both of which can be heated, are preferred, but presses and sublimation transfer pressure calenders can also be used.

After separating the transfer substrate, the fixing can be carried out the colorants (dyes) on the material to which they have been transferred, by appropriate methods to be completed. Such methods are e.g. B. heating, treating with water vapor at atmospheric pressure and treating with water vapor at high temperature, the in hot air equipment, presses, Star steam treatment equipment, Festooo steam treatment equipment, Autoclaves and ovens including steam treatment ovens, can be carried out. Monforts reactors can also be used or similar devices in which a

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dry or moistened fabric with 'a pressure felt against a heated drum is pressed can be used. In certain cases, such as B. when printing azo dyes on cotton, sufficient heating of the print can be achieved during calendering, whereby separate heating becomes superfluous.

After the appropriate fixing treatment, the polyoxyethylene compound and the other water-soluble components of the transfer layer as well as the unfixed dye by washing with water in any device or using any method, which is suitable for this purpose, removed from the printed material.

The invention is illustrated in more detail by the following examples, without, however, being restricted thereto.

example 1

A paste consisting of 1f? O S Polyethylene Glycol Compound 2OM (Union Carbide Corporation), 100 g Primal K3 (Primal Chemicals), 20 g Emulsifier 3240 (Bayer), 240 g water, g of white spirit and 40 g of Drimalan Blue F-2GL (Sandoz) by screen printing on the glazed surface of MG Litho-

graphic paper 70 s / ^m (Australian paper manufacturer) on

printed, leaving 12 g / m 2 dry paste on the printed areas of the paper. After drying, the printed paper was combined with a chlorinated smooth woven worsted fabric of 160 g / m _{2, made from a 64's quality wool y} by a Kleinewefers Ealander from

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Type K4O / 3 with a chrome-plated steel roller 2 m in length and with a diameter of 335 mm "from 100 C and a nylon counter roller with a diameter of 500 mm at a total pressure of 30,000 kg and a speed of 5 m / After the separation from the transfer paper, the fabric was ^{treated with steam for 30 minutes in an autoclave at 100 °} C. and in water at 50 ^° C., then with a 0.5 % washed ammonia solution of 50 ⁰ C and a 0.5% acetic acid solution of 50 ° C. the finished (surface-treated) fabric had a sharply defined deep blue print, in which the printed surfaces were very smooth. the authenticity of the print to washing and rub off was excellent.

Example 2

A paste consisting of 150 g Polyox WSEN-IO (Union Carbide Corporation), 100 g Dicrylan WK (Ciba-Geigy), 20 g Teric 16A29 (Imperial Chemical Industries), 240 g water, 450 g white spirit and 40 g Levafix Brilliant Yellow E3G (Bayer), was printed as in Example 1 using the screen printing process on 90 g / m MG lithographic paper, 14 g / m 2 of the dry paste remained on the printed areas of the paper. The pattern was as in Example 1 transferred to a chlorinated woolen fabric. After treatment with steam and washing out according to the example 1, the yellow print had excellent clarity and density with good fastness to washing and staining.

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Example g

The replacement of Drimalan Blue I "-2GL with Supranol Brilliant Red GW (Bayer) in the process described in Example 1, but this time the temperature of the steel calender shell 80 C and the total pressure was 20,000 kg, resulted in a red print with excellent sharpness and density and excellent fastness to bleaching and staining.

Example 4-

The replacement of 150 g Polyoxymethylene Glycol Compound 2OM by a mixture of 128 g Polyethylene Glycol I500 (Imperial Chemical Industries) and 22 g Polyox VSRIT-750 (Union Carbide Corporation) in the process described in Example 1 resulted in a slightly deeper blue print than in Example 1 with similar properties.

Example j?

When Drimilan Blue F-2GL in the printing paste of Example 1 was replaced by 100 g Contrastol V (Bayer); A colorless pattern was transferred to an untreated, smoothly woven worsted fabric of 160 g / m 2 made from 64's quality wool according to the method of Example T. The fabric was treated for 30 Hinuten at 100 ⁰ C with water vapor and then it was treated with 1.5% Verofix Red GGL (Bayer) in a bath of 2% acetic acid, 10%! Sodium sulfate and Λ% Avolan RE (Bayer) at a Fleet to material ratio of 20 Λ (all

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Percentages are based on the weight of the fabric) colored. The temperature of the bath was ^{increased from 40 to 100 °} C. within 1 hour and held at 100 ^° C. for 1 hour. The areas printed with the pattern then appeared dark red against a pale red background. The dyed pattern produced in this way was fast to washing and staining.

Example 6

When replacing Contrastöl W with Sandospace R (Sandoz) in Example 5, after dyeing, white-printed areas on a red background were obtained.

Example 7

When using 40 g Kiton Fast Orange G (Ciba) instead of Drimalan Blue F-2GL and a woven mylon fabric of

240 g / m 2 instead of the woolen fabric, a sharp, uniformly orange-colored print was obtained according to that in the example 1 described procedure.

Example 8

A transfer print was made on a woven polyester fabric of 250 g / m 2 using a with a paste printed transfer paper, 40 g of 40 g Celliton Yellow TX4-381 (BASF) instead of Drimalan Blue F-2GL in the procedure of Example 1 were used. Of the

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The dye was fixed by heating in an oven at 190 ^° C. for 1 minute instead of by steam treatment and the print was washed off as indicated in Example 1. The yellow print obtained was sharp and uniform with good fastness to washing and staining.

Example 9

The replacement of Drimalan Blue F-2G-L in that described in Example 1 Procedure by 30 g Eriochrome Cyanine R (Ciba-Geigy) and 10 g of potassium dichromate resulted in a blue print with good fastness to washing and staining.

Example 10

When using 40 g of Haxilon Red BL (Ciba-Geigy) instead of Drimalan Blue F-2GL and an acrylic woven fabric of

244 g / m instead of the wool fabric you got a sharp, light, even, red imprint with good fastness to washing and staining when using the in Example 1 described procedure.

Example 11

A mercerized cotton fabric of 120 g / m 2 was made through Padding on an aqueous solution containing 20 g / l Naphthol AS (Höchst), 20 g / l Turkey Red Oil (Victorian Chemical Company) and contained 8 g / l sodium hydroxide, with an intake of

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80% pretreated and then ^{dried at 130 °} C. A transfer paper was produced and the imprint was transferred to the fabric as in Example 1, this time Drimalan Blue F-2GL being replaced by 40 g Fast Red Salt TE (Höchst). After the melt transfer step, the development of the print at tree temperature was completed by immersing the fabric in an aqueous solution containing 5 g / L sodium bisulfite for a period of 30 seconds, and then rinsing the fabric in water by boiling in a solution containing Contained 3 g / l Lissapol ND (ICI) and 2 g / l sodium carbonate, soaped off, rinsed in cold water and dried.

Claims (1)

2850003 709-Dr .. T Applicant: COMMONWEALTH SCIENTIFIC AND INDUSTRIAL RESEARCH ORGANIZATION Limestone Avenue, Campbell, Australia Patent claims 1. Coloring or paste preparation for use in Melt transfer printing characterized in that it contains or consists of (i) a melt transfer medium comprising at least one derived from a cyclic ether Polymers, (ii) at least one colorant or dye and (iii) water. 2 * Preparation according to claim 1, characterized in that component (i) consists of a polymer or a mixture of polymers of ethylene oxide of the general formula R (OCH ₂ CH ₂ ) J ₁ OR ¹ , where η is the average number of oxyethylene groups per Specifies molecule of the polymer or the polymer mixture and has a value within the range of 10 to 100,000, R and R ¹ , which are the same or different from each other, each represent hydrogen or an alkyl group having 1 to 18 carbon atoms. 3. Preparation according to claim 2, characterized in that η has a value within the range of 300 to 3000 909822/0733 ORiGlNALlNSf ³¹ ECtH) and R and R ^{1 are} hydrogen or methyl or ethyl groups. A-. Preparation according to one of Claims 1 to 3, characterized characterized in that the polymer or the polymer mixture makes up 5 to 4-0% by weight of the preparation. 5. Preparation according to claim 4-, characterized in that the polymer or the polymer mixture makes up 10 to 20% by weight of the preparation. 6. Preparation according to one of claims 1 to 5, characterized in that the colorant or the dye 0.01 to 20% by weight of the preparation. 7. Preparation according to one of claims 1 to 6, characterized in that it also contains one or more of the contains the following components: (iv) thickeners, (v) Agents used to achieve color development or fixation of certain dyes or dyes are required, (vi) printing auxiliaries to improve the quality of the prints on the substrate, (vii) substances which increase the durability of the printed layer on the substrate, and (viii) Substances that give the transfer printed material special properties. 8. Preparation according to claim 7 »characterized in that 909822/0733 a thickener (iv) is used, the white spirit in an amount of 5 to 55 wt.%, Based on the weight of components (i), (u) and (iii), and 0.1 to 5% by weight of an emulsifying agent, based on the same Base, contains. 9. Printing medium for melt transfer printing, characterized in that it contains or consists of one A substrate which is coated or printed with a preparation according to one of the preceding claims. 10. Print medium according to claim 9, characterized in that the substrate is paper. 11. Process for printing on knitted, woven and non-woven fabrics and film materials, such as e.g. B. Mushrooms and films that contain a component made with water-soluble or water-dispersible dyes can be colored or printed and on which the dyes by heating and by steam treatment be fixed by melt transfer printing, in which one (1) the material to be printed with a substrate coated or printed with an ink or paste brings in contact, (2) the dried coating or imprint from the substrate transfers to the material to be printed using heat and / or pressure, (3) the fixing of the colorants or dyes in the layer transferred onto the material to be printed by heating or by treatment with steam 909 8 22/0 733 completed and (4) the transfer printed material with water washes to remove soluble residue from the transfer layer and any unfixed residue Dye or dye, characterized in that it is used as a paint or paste
a preparation according to any one of claims 1 to 8 is used. 12. The method according to claim 11, characterized in that in step (2) a temperature within the range from 30 to 150 ⁰ C and / or a pressure within ο
of the range from 1 to 200 kg / cm. 909822/0733