DE2325308A1 - INK CARRIERS FOR THE THERMAL TRANSFER PRINTING METHOD AND ITS USE FOR PRINTING PRINT CARRIERS, IN PARTICULAR TEXTILE AREAS - Google Patents

Description

DAI NIPPON PRINTING CO., LTD.,
Tokyo, Japan

"Ink carriers for the thermal transfer printing process and their Use for printing on print media, in particular flat textiles "

Priority: May 19, 1972 _S Japan, No. 49 136/72 · ·; '20. March 1973, Japan, No. 31 440/73

The invention relates to ink carriers for the thermal transfer printing process and their use for printing print media, in particular flat textiles,. ". that deal with them Let dye carriers dye in pure shades and good fastness properties. -

Various methods are known for printing print media, in particular flat textiles. Present in strips Textile fabrics are printed with a wide variety of printing machines. Recently, that too has been so-called transfer printing process known, also known as thermal transfer printing process or sublistatic process is called, in which the dyes by diffusion and sublimation of printed intermediate or auxiliary carriers. hereinafter referred to as Ink carrier denotes, especially paper webs, on which

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printing material can be transferred. Such thermal transfer printing processes are in US-PS 3,363,557, d ^ r GB-PS 951,987, · the FR-PS 1 223 330 and the CH-PS 476 893 described. Further H. Küpper wrote in an essay "The printing rustled Womenswear and menswear fabrics using the sublistatic method "in Melliand Textilberichte 8/1971, pp. 9 ^ 9 to 950 about this process reported. ·

In this process, a color carrier, for example on-Pr.-. pier _r applied a printing ink, the main component of which contains a dye, for example a disperse dye or an oil-soluble dye, which sublimes easily. Then the surface of the ink carrier that has the printing ink is brought into contact with the material to be printed. the color being transferred to the material to be printed on at the appropriate temperatures. The process has the advantage that the dyeing is carried out by applying dry heat and the usual printing, steaming or ash steps can be dispensed with.

The known thermal transfer printing processes, however, have the disadvantage that the dyes are generally only sublimable Disperse dyes can be used. Therefore this method is only applicable to certain print media. "

Textile fabrics dyed with disperse dyes' are mainly textiles made from synthetic polymers such as polyester, polyamide-6,6, and polyacrylonitrile Cellulose triacetate. The Therrno-Tranni'e.-

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ORIGINAL INSPECTED

printing process especially for textiles made of polyester, because these polycondensates have a high level of heat resistance. Textiles made from polymers whose melting points are too low, such as polyvinyl fibers, polypropylene, and to some extent Polyamide-6 and -11 cannot be printed with disperse dyes using the thermal transfer printing process. The same goes for for textiles made of natural fibers, such as silk, wool and cotton, which are mixed with disperse dyes !! do not stain permit.

If one tries, therefore, the range of after the thermal transfer printing process To expand substrates to be printed, dyes other than disperse dyes must be considered draw. However, these dyes are practically unable to sublime in the heat. Even if you are using these dyes performs the thermal transfer printing process, it is difficult to obtain colored products of good quality. Furthermore, this thermal transfer printing process has the disadvantage that the sublimation fastness of the printed substrates is unaffected. is peaceful. Since in the thermal transfer printing process the sublimable Dye diffuses into the fibers of the substrate,

it is activated again when the colored material is heated and can thus sublime out of the material again. This has the disadvantage that the colored material loses dye and the dye discolors other substrates.

The object of the invention is to provide ink carriers for the thermal transfer printing process to create, with which colored printing media, like textile fabrics, in very pure colors

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and good fastness properties, in particular sublimation fastness, can be produced, and with which the range of printable Materials is expanded. Another object is to use a method of thermal transfer printing to provide the color carrier. These objects are achieved by the invention.

The invention is based on the finding that when treating a basic dye with poor color transfer properties properties that are based on phenomena such as melting, evaporation or sublimation when heated, with one Oxidizing agents the ¥ arraetransmission property of the basic Dye temporarily increased v / ground. This is an extension of what can be printed using the thermal transfer printing process Materials result. As soon as the dye has passed into the material to be printed, it is again as basic dye in its original form, it has superior fastness properties and is therefore obtained a nicely colored material in very pure shades.

The invention accordingly relates to color carriers for the TherEO color transfer process, which consist of a carrier consist on which a pattern of a basic dye with poor heat transferability, an oxidizing agent to increase animal transferability of the basic dye in the heat and a binder is applied.

The invention also relates to a method for thermal transfer printing, which is characterized by the fact that a coloring

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carrier on which a pattern of a basic dye with poor transferability in heat, an oxidizing agent to increase the transferability of the basic dye in the heat and a binder is applied with which to Bringing the printing material into contact, the build-up under pressure heated and then removed the ink carrier from the printed material. -

The invention is further elucidated below.

Examples of those which can be used according to the invention. Carriers under the different conditions for the production of the patterns and the thermal transfer printing process are not affected, are different papers and refined papers, such as machine coated Papers, cell glass, foils and plate material made from various thermally stable polymers, metal foils and metal plates and metal foils made with various Straps are laminated.

The basic dyes which can be used according to the invention include the so-called basic dyes and cationic ones Dyes. Examples of basic dyes used for the color carriers of the invention are basic dyes and cationic dyes which were not used in the known thermal transfer printing processes and which due to such appearances as melting, evaporation, or Sublimation in the heat) a relatively poor transferability in the heat of thermal transfer printing. The aforementioned dyes are, for example, basic methine dyes

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substances (cyanine dyes) or cationic dyes, such as monomethine, dimethine or trimethine dyes, for example 3,3'-diethyloxacyaninjodid, astrazon pink FG (CI. 48015), 2,2 «-carbocyanine (CI. 808) ,. Astraphloxin FF (CI. 48070), Astrazon yellow. 7GLL (CI. Basic Yellow 21), Aizen Cathilon Yellow 3GLH (CI. 48055) and Aizen Cathilon Red 6BH (CI. 48020); basic diphenylmethane dyes and cationic dyes such as auramine (Cl. 655); basic triphenylmethane dyes and cationic dyes such as malachite green (CI. 42000), brilliant green (CI. 42040), magenta (CI. 42510), methyl violet (CI 42535), crystal violet (CI. 42555), methyl green (CI. 684) and Victoria blue B (CI. 44045); basic xanthene dyes or cationic dyes such as pyronine G (CI. 739), rhodamine B (CI. 45170) and rhodamine 6G (CI. 45160) ; basic acridine dyes or cationic dyes such as acridine yellow -G (CI. 785), Rheomine AL (CI. 46075), benzoflavin (CI. 791) and phosphine (CI. 46045); basic quinone imine dyes or cationic dyes, such as neutral red (CI. 50040), astrazone blue BGE / X 125 % (CI. 5IOO5) and methylene blue (CI. 52015) and other basic or cationic dyes such as anthraquinone dyes with quaternary ammonium groups.

The oxidizing agent used in the color vehicles of the invention increases the heat transferability of the basic dye to the material to be dyed. Specific examples suitable oxidizing agents are permanganic acid and theirs Salts such as sodium and potassium permanganate, chromic acid and similar compounds such as potassium chromate, potassium dichromate,

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Sodium and ammonium chromate, sodium and ammonium dichromate,

chromate magnesium and calcium chromate, potassium chloro * and chromyl chloride, Peroxides, such as hydrogen peroxide, sodium, barium »and calcium peroxide, and nitrates, such as sodium, potassium and Ammonium nitrate. .

The oxidizing agent is preferably used in an amount of 0.1 to 20, especially 1 to 10 molar equivalents per molar equivalent of the basic dye is used.

The ink carrier can be produced by various methods. For example, you can use a printing paste that consists of a Binder, the basic dye and an oxidizing agent as the main ingredients, on a carrier in a monochrome or multicolored pattern, e.g. letters, Apply surfaces and picture elements with the usual printing methods or by drawing or painting. One can also a printing paste, the main ingredients of which are a binder and contains a basic dye, initially on a carrier in a single-colored or multicolored pattern according to the usual Apply printing methods or by drawing or painting, and then apply to this ^ pattern an agent known as Main component that contains oxidizing agents. Furthermore, an agent can first be applied imagewise to the carrier, which contains the oxidizing agent as the main component and then image-wise apply a printing paste to this pattern, the main components are the binder and the basic Contains dye. In this way, a monochrome or multicolor pattern can be formed on the support, and et; ·

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creates a color carrier on which the basic dye and the oxidizing agent in the. Parts of the image are present. As a further Alternatively, you can use a color paste, which contains a binder and a basic dye as the main components and which has been previously treated with an agent that is the main ingredient contains an oxidizing agent, by customary printing methods • or by drawing or painting to form a Apply monochrome or multi-colored pattern to a carrier. The way of making the dye carrier depends on the The type of intended use. The pattern on the carrier can be a continuous layer that contains the basic Contains dye and the oxidizing agent.

Examples of binders which can be used according to the invention for production of the color carrier are the usual binders, such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, Cellulose acetate, cellulose butyrate and sodium alginate and their derivatives, polyvinyl alcohol, polyvinyl acetate, polycarbonates, Polyesters, polyamides, phenolic resins, amino resins, homopoly-

merizates and copolymers from a wide variety of monomeric vinyl compounds, such as unsaturated carboxylic acids, e.g. acrylic acid, Methacrylic acid, itaconic acid, fumaric acid and maleic acid or their esters, nitriles or amides, vinyl chloride, vinylidene chloride, Vinyl acetate, styrene, vinyl pyrrolidone, methyl vinyl ether, butadiene, ethylene and propylene, starch, gum arabic, Tragacanth and gelatin.

Such binders are used to make the ink carriers of the invention not preferred, which at the temperature of the thermo-

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Transfer printing process soften or melt. Using Such binders will also transfer them to the material to be printed. When printing flat textiles this results in products with a poor grip.

For the production of the ink carrier of the invention can also Binder, the basic dye and your oxidizing agent can also be used in addition to a dyeing aid, the Thermal transfer printing brings in the material to be printed and the micelles swell, which increases the penetration capacity of the basic dye is increased. Furthermore, "other additives can be used to improve the behavior." Control the color paste from the basic dye, binder and oxidizing agent.

Specific examples of dye auxiliaries that can be used are urea, Naphthalene, ammonium tartrate, thiodiethylene glycol,

Salts of oxalic acid with aliphatic amines, such as cyclohexylamine, ammonium acetate, benzylamine and various anionic, nonionic and amphoteric surfactants.

Other auxiliary materials include e.g. plasticizers, stabilizers, Waxes, fats, drying agents, auxiliary drying agents, hardeners, emulsifiers, agents for increasing viscosity, fillers and dispersants.

The mixture of basic dye, oxidizing agent and binder can be in any form, e.g. as a solution, emulsion, suspension or sol.

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When superimposing the color carriers of the invention in their Storage it can happen that a pattern from one color carrier is deposited on the carrier of the other color carrier. this has the consequence that the concentration of the basic dye in the ink carrier gradually decreases and when printing the The hue obtained is no longer pure. In the worst case, the ink carrier has become unusable «To avoid this effect; * the dye carriers of the invention are preferably produced in such a way that a pattern of the basic dye, the oxidizing agent and the binder produced and then on this pattern a top layer of one Synthetic resin is applied, which the basic dye cannot penetrate during storage, while it is through this top layer goes through during thermal transfer printing. In this way, the disadvantages described above can be avoided, and the storage time of the ink carriers can be extended considerably.

Specific examples of synthetic resins which can be used to produce the top layer with the aforementioned properties are sodium polyacrylate, polyvinyl alcohol, mayprogum, dextrin, methyl cellulose, carboxymethyl cellulose. Polyvinylpyrrolidone, vinyl methyl ether-acrylic acid copolymers, water-soluble, thermosetting acrylic resins, with colophon. nium-modified maleic acid ester resins, phenolic resins modified with colophony, xylene resins, polyacrylic acid esters, butyral resins, epoxy resins and polystyrene. These film-forming resins can be prepared by conventional coating methods, ZE * by means of gravure or screen printing method, V, ^r alzenauftrag-

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- ■ ORIGINAL INSPECTED

Process with which a squeegee, air knife or spray gun are applied. The area applied depends on the type of synthetic resin; it is preferably 0.2 to 4.0 g / V ". are preferably used for the top layer water-soluble polymers, _L such as polyvinyl alcohol, sodium polyacrylate and polyvinylpyrrolidone, and oil-soluble resins such as xylene resins, modified with Cölophonium phenolic resins, polyvinyl butyral, epoxy resins, polystyrene and petroleum resins These resins not only avoid

Carrier
soiling of the / but also does not interfere with thermal transfer printing of the basic dye _} and patterns with sharp contours can be produced. -

In the manufacture of these modified ink carriers of the invention, monochrome or multicolored patterns, e.g., letters, Areas and picture elements, in the usual "way with the invention composite printing paste applied. As an alternative, you can also use the usual method on the ink carrier monochrome or multi-colored pattern with an inventive Apply composite color paste or first apply an agent imagewise to the carrier, which as the main component contains the oxidizing agent, and then apply a color paste to this pattern, which contains the basic B'your dye and contains the binder. As a further alternative, the basic dye can first be treated with an agent which contains the oxidizing agent as the main constituent, whereupon a monochromatic image is formed on the support in the usual way or multicolored pattern using a printing paste based on the above as the main ingredients described way treated basic dye and that

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Contains binding agent. Finally, the ink carrier obtained can be applied in the manner described above, e.g. Coating with the help of gravure printing or screen printing, Apply the top layer of synthetic resin to the pattern with the squeegee or air knife. One can also use color carriers of the invention produce by covering them with a sheet or plate of 'a synthetic resin through which the basic dye is placed Normal conditions cannot pass through, conceals.

Depending on the type of carrier material, the basic dye can pass through this carrier material. In this case is'der carrier initially with a primer layer of a Coated synthetic resin through which the basic dye and the oxidizing agent cannot pass under normal conditions can. A pattern is then made on this primer layer applied to the basic dye and the oxidizing agent. Finally, the ink carrier is covered with a top layer of a Synthetic resin provided.

Specific examples of synthetic resins for the primer layer are Polyvinyl alcohol, sodium polyacrylate, polyacrylic acid amide, mayprogum, dextrin, methyl cellulose, carboxymethyl cellulose, Polyvinylpyrrolidone, vinyl methyl ether-acrylic acid copolymers, water-soluble, thermosetting acrylic polymers, British guimi, casein, crystal gum, gum arabic, tragacanth ■ Esters of polyhydric alcohols from rosin, with rosin modified phenolic resins, hard synthetic resins, ... such as xylene resins, Acrylic acid ester resins, butyral resins, epoxy resins, acetyl-butyryl cellulose and thermosetting acrylic resins. Particularly preferred

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are water-soluble synthetic resins such as sodium polyacrylate, polyvinyl alcohol, Dextrin \ md polyvinylpyrrolidone and oil-soluble Resins such as phenolic resins modified with colophonium, xylene resins, polyvinyl butyral, epoxy resins, polystyrene and petroleum resins. The surface application depends on the type of synthetic resin. It is preferably 0.2 to 4 g / m 2. The coating can in the usual catfish, e.g. with the help of gravure or Screen printing process or with the air knife.

The production of the aforementioned ink carrier can be carried out, for example, by Application of the primer layer to the carrier. Or by lamination a film made in a known manner from the synthetic resin on the carrier with the formation of a primer * , layer and subsequent application of the invention composite color paste and the top layer will.

When using aluminum foils, synthetic resin foils or plates, Rubber sheets, very high density glassine paper or parchment paper as a carrier it is ^ not necessary on this To apply a primer layer to carrier materials.

To make the color carriers of the invention / two or more Priming layers or top layers or laminations made from the aforementioned synthetic resins are applied to the carrier, through which the basic dye and the oxidizing agent cannot pass under normal conditions. At the .Application of the top layer must of course be taken to ensure that that the pattern is not damaged. The Therino transfer printing process using the invented

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correct color carrier explained.

First, the surface of the pattern or the top layer of the ink carrier is brought into contact with the material to be printed. The structure is then heated under pressure between two heated plates or passed under pressure between two heated rollers. In this way, the basic dye, but not the oxidizing agent and the binder ■ tel. transferred to the material to be printed. The ink carrier is then removed from the printed material. In this way, a printed material is obtained which contains only the basic dye in very pure shades and good fastness properties. In the thermal transfer printing process, the heating temperature does not have to be higher than the melting point or sublimation point of the basic dye used in the ink carrier. The heating temperature depends on the kind of the basic dye. It is preferably in a range of about 80 to 25O ⁰ C. The applied pressure is preferably about 50 g / cm to 20 kg / cm. The heating and pressing time is preferably about 30 to 90 seconds,

In the method according to the invention, it is also possible to use a paint carrier of the invention which, on its entire surface, the color layer is provided with a mask which covers non-printing areas and leaves printing areas free. Then the material to be printed is brought into contact with the mask and the entire structure is heated under pressure.

Examples of masks that can be used are masking paper or

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- foils or stencil paper that is suitable for processing by hand, typewriter or ballpoint pen, heat-sensitive stencil paper on which a pattern of letters, Areas or picture elements is applied, screen printing forms which have a pattern, foils and plates made of different Synthetic resins, paper and various metal foils and thin metal plates with letters, surface or image patterns are provided by stamping or etching processes.

In addition to the aforementioned mask, you can also use dry-to-apply photosensitive films such as * the Liston film (Du Pont) and Raminer-FiIm (Dyanachem) use those with "a Patterns are provided by exposure, developing and fixing.

With the ink carriers of the invention can after the thermal transfer printing process According to the invention, a wide variety of materials can be printed, e.g. textile sheet-like structures Natural fibers such as cotton, hemp; wool and silk, glass fibers, Regenerated cellulose, cellulose acetate, polyamides, polyesters, polyacrylonitrile, polypropylene, polyvinyl chloride and polyvinyl alcohol, foils and sheet materials made from a wide variety of materials Polymers, papers of all kinds, foils and plates made of all kinds of metals, glass plates, earthenware and porcelain, leather, collage and artificial leather, rubber sheets and molds, wood, plywood, slate, cardboard, plasterboard and laminates made from organic and inorganic compounds.

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The thermal transfer printing process can be carried out in a simple manner with conventional heating plates, heated presses or calenders and be carried out under pressure. After printing, the printed material can be treated with superheated steam or acid and superheated steam It is noteworthy that the treatment time, namely the time for complete coloring with the basic dye, is significantly shorter than with the conventional printing process usual printing pastes.

The color carriers of the invention have the advantage that with you materials according to the thermal transfer printing process

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that can be printed with / not at all with basic Have dyes printed. As with the known thermal transfer printing process only disperse dyes can be used, the textile material was essentially polyester textile material limited. On the other hand, by suitable choice of the basic dye in the dye carrier, such textile material can be added

c? -? r invention of the thermal transfer printing process / be printed, which suitable for dyeing with this basic dye. If the suitable basic dyes are used, it is thus possible Printing on textile fabrics e.g. made of polyacrylonitrile or natural fibers such as silk and wool.

The color transfer of the basic dye in the heat can be increased according to the invention by the per se The dye, which is poorly suited for the thermal transfer printing process, is treated with an oxidizing agent. Once the dye has passed over to the material to be printed

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it is back in its original form. The colored material has excellent fastness properties, e.g. weather resistance, abrasion resistance, heat resistance as well Resistance to solvents, water and chemicals. A subsequent treatment with superheated steam will still get purer shades. ■

The ink carriers of the invention have the advantage that their storage time and handling is improved and the risk of discarding when stacking the ink carriers is reduced.

The examples illustrate the invention. Unless otherwise stated, parts are by weight.

. B e i s ρ i e 1 1

100 parts of polyvinyl butyral (Eslex BL-1) are in 900 parts a mixture of xylene and ethanol (7: 3) dissolved. 900 parts of the solution obtained are mixed with a solution of 50 g of sodium dichromate in 50 ml of water (pH 3.2) with thorough stirring. solved. 900 parts of the mixture and 100 parts of Aizen Cathilon Blue 5G (CI, 51005) ground carefully in a ball mill. A blue printing paste is obtained. ■

Using Aizen Cathilon Red'6BH (CI. 48020) resp. Aizen Cathilon Yellow 3GLH (CM. 48055) a red and a yellow printing paste is produced in the same way. Under use of the blue, red and yellow printing paste obtained , an ink carrier for a multi-color print produced by,

that you can print a pattern by gravure printing on gravure ^{: 309848/1002}

vpaper prints. The paper ink carrier obtained is hereby placed with a fabric * made of polyacrylonitrile fibers with a thickness of 0.4 mm and the structure is heated to 190 ° C. for 60 seconds between heated plates. After peeling off the paper color carrier, you get a fabric dyed in deep and pure color tones. The printed fabric obtained is reacted with an ecru woven fabric of polyacrylonitrile into contact and heated 15 seconds at a 180 ⁰ C. This test gives a sublimation fastness with a value of 4 to 5 · The off-white fabric was not stained. The _; The lightfastness of the blue, yellow and red colors shows the value 5, 6 and 3, respectively. It can therefore be described as good. Fastness to washing, fastness to rubbing and

to have. Resistance to chemical cleaning agents / the value 5.

Thus, the dyed fabric has good fastness properties.

The example is carried out with the dyes listed below "■ * repeated. Similar results are obtained:.

(a) Aizen Basic Cyanine 6GH
(CI. 42025; color turquoise)

(b) Aizen methylene blue FZ

(C.I. 52015; shade blue)

(c) Aizen Cathilon Brilliant Yellow 5GLH (CI. Basic Yellow 13; color yellow)

(d) Astrazon red 6B

(CI. 48020; color red)

(e) Aizen Cathilon Orange RH
(CI. 48040; shade orange)

(f) Aizen malachite green

(CI. 42000; shade green)

(g) Aizen Cathilon Brilliant Pink BF (CI. Basic red 36; red tone pink)

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(h) Astraζon Pink FG

(CI. 48015; shade pink)

(i) Astrazon Blue BGF / X 12Ο? 6

(CI. 51005; shade turquoise)

(j) Mixture of Aizen Cathilon Blue 5G

(CI. 51005) and Aizen Cathilon Yellow 3GCH

(CI. 48055) in a weight ratio of 1: 1; Shade of green

(k) Mixture of Aizen Cathilon Blue 5G (CI. 51005) and.

Aizen Cathilon Red 6BH (CI. 48020) in a weight ratio of 4: 6; Shade purple -

(1) Mixture of Aizen Cathilon Red 6BH (CI. 48020) and

Aizen Cathilon Yellow 3GCH (CI. 48055) in weight ratio 2: 8; Shade of orange.

When using the aforementioned basic dyes in color carriers without oxidizing agents for the thermal transfer printing process, unsatisfactory results are obtained.

Example 2

90 parts of ethyl cellulose (ethyl cellulose N7CP), 90 parts of Aizen Cathilon Red 6BH (CI. 48020) and 90 parts of potassium dichromate are used registered in 770 parts of a mixture of xylene and ethanol (8: 2), and the mixture is v / ird in a ball mill carefully wed. A red color paste is obtained. the after the gravure printing process imaged on gravure paper is printed. The resulting paper ink carrier has similar properties to the paper ink carrier produced according to Example 1.

If potassium permanganate is used instead of potassium bi-chromate, similar results will be obtained.

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Example 3

950 parts of a 15 percent aqueous solution of polyvinyl. alcohol (Gohsenol GSS1173) are mixed with 50 parts of araraonium dichromate carefully mixed. 900 parts of the preserved aqueous Solution of ammonium dichromate and 100 parts of Aizen Catbilon Blue 5G (CI. 51005) are then carefully ground in a ball mill. The blue color paste obtained is after Screen printing process imprinted imagewise on gravure paper. The thermal transfer printing process is used with the paper ink carrier obtained according to example 1 repeated. A printed fabric with good properties is obtained.

Example 4

100 parts of the ethyl cellulose used in Example 2 and 100 parts of Astrazon Blue BG E / X are mixed with 800 parts of a mixture from xylene and butanol (8: 2) carefully ground in a ball mill. A blue color paste is obtained which is imprinted imagewise on gravure paper with a rotogravure printing machine. ■

6 parts of potassium dichromate are dissolved in 94 parts of a 4 percent aqueous solution of methyl cellulose (Metolose 65SH50). The resulting solution is applied to the dye layer using a doctor blade (Mayerbar No. 4). The top layer is then dried. The paper color carrier obtained is reacted with a fabric of polyacrylonitrile! Fibers of a thickness of 0.4 rnm brought into contact and heated for 60 seconds under pressure between heating plates to 190 ⁰ C. A fabric dyed in a deep blue shade is obtained.

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Example 5

100 parts of sodium dichromate are dissolved in 900 parts of a 15 percent aqueous solution of the polyvinyl alcohol used in Example 3. A paper with a basis weight of 55 g / m 2 is coated with this solution in a gravure printing machine. The surface application is 3 g / m. The one produced in Example 4 is imagewise onto this green layer
blue color paste applied. The thermal transfer printing process according to Example 4 is carried out using this paper color carrier. Similar results are obtained.

Example 6

100 parts of the ethyl cellulose used in Example 2,
100 parts of Aizen Cathilon Red 6BH, 20 parts of sodium dichromate
and 20 parts of water / water are mixed together with 760 parts of a mixture of xylene and butanol (8: 2) in a ball mill
carefully wed. A red color paste is obtained, which is printed onto gravure paper using a rotogravure printing machine.

6 parts of urea are in 94 parts of a 15 percent strength

GL-O5
aqueous solution of polyvinyl alcohol / dissolved. The aqueous polyvinyl alcohol solution is applied to the dye pattern layer
With the help of a squeegee (Mayerbar No. 4) applied as a top layer. A paper ink carrier is obtained which is brought into contact with a fabric made of polyacrylonitrile fibers and takes 45 seconds

ο will

heated in an ironing press to 190 C /. The received printed Fabric is colored in a deep, pure, red shade. The use of urea increases the permeability of the dye into the tissue and the color development

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significantly improved.

Example! 7th

Using the oxidizing agents mentioned below, color pastes are made from basic or cationic dyes Dyes made in a ball mill. Then they will Color pastes printed on a color carrier, which was very suitable for the thermal transfer printing process.

(a) Chromium trioxide. "

10 parts of chromium trioxide ground in 90 parts of a 4 percent strength aqueous solution of the methyl cellulose used in Example 4 solved. After adding 10 parts of Aizen Cathilon Red 6BH 90 parts of this solution, the mixture is ground thoroughly in a ball mill. A red color paste is obtained from which a paper ink carrier is produced.

(b) potassium nitrate

The ingredients listed below turn into a green one

Color paste produced, which is applied to paper as a color carrier will:. 'Ethyl cellulose. '100 parts

Potassium nitrate . , ' 100 parts malachite green 100 parts

Xylene 56 parts

Butanol - 14 parts

Similar results were obtained with sodium nitrate instead of potassium nitrate obtain..

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(c) hydrogen peroxide solution

A gel paste is made from 100 parts of the in Example 2. used ethyl cellulose, 100 parts Aizen Cathilon Yellow 3GLH and 800 parts of a device made of xylene and butanol (8: 2). Then 4 parts of an aqueous ■ Hydrogen peroxide solution in 96 parts of a 40 percent strength dissolved aqueous solution of methyl cellulose. This solution is applied to the paint layer with a doctor blade (Mayerbar No. 4) as a top layer applied. A paper color carrier is obtained.

(d) potassium chromate.

800 parts of a 12 percent solution of ethyl cellulose in a mixture of xylene and ethanol (7: 3), 100 parts of malachite green, and 100 parts of a saturated at 25 ⁰ G aqueous solution of potassium chromate are ground thoroughly in a ball mill. The green color paste obtained is applied in a pattern to a carrier. An ink carrier for the thermal transfer printing process is obtained.

Similar results are obtained using ammonium aurachromate obtained instead of potassium chromate.

(e) sodium permanganate

100 parts of sodium permanganate in 90 parts of a 4 percent strength dissolved aqueous solution of methyl cellulose. This solution is mixed with 100 parts of Aizen .Cathilon Blue 5G and grind carefully in a ball mill. You get a blauo Color paste that is applied to a gravure paper. Man receives a paper color carrier.

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(f) Anhydrous barium peroxide

100 parts of anhydrous barium hydroxide are converted into 900 parts registered a 4 percent aqueous solution of methyl cellulose and ground thoroughly in a ball mill. 900 parts 100 parts of Aizen Cathilon Red 6BH are added to the dispersion obtained and carefully put in a ball mill marry. The red color paste obtained is printed on gravure paper applied

(g) magnesia dichromate

100 parts of magnesium chromate are in 900 parts of a 4 percent strength dissolved aqueous solution of methyl cellulose. 900 parts of this solution are mixed with 100 parts of malachite green and grind carefully in a ball mill. The green color paste obtained is applied to gravure paper. You get a paper color transfer for the thermal transfer printing process.

(h) Mixture of anhydrous barium peroxide and sodium bicarbonate

chromate ■. ,

50 parts of anhydrous barium peroxide and 50 parts of sodium dichromate are introduced into 900 parts of a 4 percent aqueous solution of methyl cellulose and thoroughly mixed. Then 900 parts of the mixture obtained are mixed with 100 parts of Aizen Cathilon Red 6BH and carefully put in a ball mill marry. A red color paste is obtained, which on Gravure paper is applied.

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(i) Geraisch made from sodium permanganate and magnesium chromate 50 parts of sodium permanganate and 50 parts of magnesium chromate v / ground in 900 parts of a 4 percent aqueous solution of methyl cellulose solved. 900 parts of this aqueous solution are mixed with 100 parts of Aizen Cathilon Blue 5G and in a Grind the ball mill carefully. The obtained blue color paste is applied to gravure paper.

Example 8

80 parts of crystal violet (CI. 42555) are dissolved in 1720 parts of water and cautiously with. 200 parts of a 20 percent aqueous solution of sodium diehromat are added. When the addition is complete, the solution is left to stand. The precipitate formed is filtered off, washed and dried. Then 70 parts of the oxidizing agent-treated crystal violet and 120 parts of the ethyl cellulose used in Example 2 are mixed with 810 parts of a mixture of xylene and butanol (8: 2), and the mixture is ground thoroughly in a ball mill. A violet color paste is obtained, which is applied in a pattern to gravure paper using a gravure printing machine. The paper color carrier obtained is reacted with a fabric made of polyacrylonitrile fibers into contact and heated for 60 seconds between heated plates to 19Q ⁰ C. A fabric dyed in a deep purple hue is obtained.

Example 9 Lightweight, machine coated paper with a The basis weight of 64 g / m is patterned in a deep-

309848 /

printing machine with a yellow, red and blue color paste of the the following composition printed. A multicolored paper carrier is obtained.

(a) Yellow color paste Aizen Cathilon Yellow 3GLH polyvinyl butyral (Eslex BL-1)

Water xylene-ethanol (7: 3)

all in all

100 parts 100 parts

45 pieces

45 parts 710 parts parts

(b) Red coloring paste Aizen Cathilon Red 6BH polyvinyl butyral (Eslex BL-1)

Water xylene-ethanol (7: 5)

all in all

100 parts 100 parts 45 parts 45 parts 710 parts parts

(c) Blue printing paste

Aizen Cathilon Blue 5G ' (Eslex BL-1) - 100 Parts Polyvinyl butyral 100 Parts Na ₂ Cr ₂ O ₇ 45 Parts water : 3) '■ 45 Parts Xylene ethanol (7 all in all 710 Parts 1000 Parts

9848 / 1-0 0

The printing speed "is 30 m / minute.

The color carrier is then treated with a 15 percent aqueous Coated solution of the polyvinyl alcohol used in Example 3 in a rotogravure printing machine. The printing speed is 20 m / minute to achieve perfect drying. The area application is 1.2 g / m ".

The filing of the paper color carrier with the top layer in the course of time when the paper color carriers are stacked on top of one another comes with the filing of stacked paper color carriers compared that have no top layer. The topcoated paper ink carrier of the invention exhibits shelf life from about 3 months and one about 3 to 4 maH longer shelf life compared to a paper ink carrier without top layer. Similar results v / ground with paper. Ink carriers get a top layer with a surface application of about 2 g / m, and in which the top layer consists of two layers of sodium polyacrylate, polyvinylpyrrolidone or polyvinyl alcohol and a butyral resin or polystyrene instead of water-soluble polyvinyl alcohol.

With the paper ink carrier produced according to the invention the thermal transfer printing process is carried out as follows:

The paper color carrier is brought into contact with a web of Polyacrylnitrilfacern with a thickness of 0, h .mm

309848/1002

and heated between hot plates at 190 ° C for 75 seconds. Then the paper color carrier is peeled off. Fabrics are obtained which are dyed in pure yellow, red and blue shades. The printed fabrics obtained have good fastness properties. In the test according to the Japanese Indus / tri enormously is the value for the washing fastness 5, for the rubbing fastness 5 and for resistance to chemical cleaning agents 5. The sublimation has long been used in 15 seconds heating at 1.80 ⁰ C a value of 4 to 5

Example 10

Example 9 is repeated, but instead of the water-soluble Synthetic resin for the top layer a polyvinyl butyral resin (Eslex BL-1) is used, which is a mixture of Toluene and alcohol is dissolved to a 15 percent solution. The surface application is about 2.0 g / m.

The resulting paper / paper ink carrier has similarly good properties in terms of shelf life and printability like the ink carrier produced in example 9.

When using oil-soluble synthetic resins such as polystyrene, epoxy resins, Petroleum resins and xylene resins in place of the polyvinyl butyral resin will give similar results.

Example 11 The primer coating solutions mentioned below also apply

Paper with a basis weight of 55 g / m "on a rotogravure rotary press at such speed au.fgci.ra-

3098A8 / 1002

conditions that perfect drying is achieved. The surface application is 2 to 3 g / m 2. The paper provided with the primer layer is then printed with the color paste prepared in Example 9 according to Example 9 using a rotogravure printing machine. A multicolor paper paint carrier is obtained. A cover solution of the composition mentioned below is then applied to the printed surface of the paper ink carrier according to Example 9. The weight per unit area of the top layer is 1 to 2 g / m ² .

The durability of the paper ink carrier with the primer layer and the top coat is compared to that of a paper ink base without a primer coat and top coat.

Test methodology: - ■

The paper-ink carrier is with the dye side with a white paper (No. 1 paper). Likewise will the unprinted surface of the paper ink carrier, i.e. the back, with a white paper (paper no.2) in con-

/ placed between? ifei glass plates tffkt. The construction is then carried out in a block tester /

/ and a thickness of 5 kg / cm ² / / extent of / and stored for 3 months at 30 ° cT ^. Then "is dar | / -> bre-

the .

gens the color on / papers No. 1 and 2 by comparison with untreated white papers No. 1 and 2 determined.,.

With the paper color carrier without a primer layer and without a top layer Test papers No. 1 and 2 are extremely discolored. In contrast, the paper color carriers with primer layer and top layer show good durability and practically no discoloration can be observed in the test papers.

309848/1002

The thermal stability of the paper color carrier with, primer layer and top layer is just as good as in the case of the paper color carrier of Example 9 _r. And a fabric dyed in pure color shades is obtained.

The composition of the coating liquids for the The primer coat and top coat are summarized in Table I. .

Table I. No, primer layer fluid. Surface liquid

1 15 percent aqueous lo- 15 percent aqueous solution sung- from polyvinyl alcohol from polyvinyl alcohol

2. "15 percent solution; by Poly

vinyl butyral in a mixture of toluene and isoprotic anol (7 t 3)

3 15 percent solution of. 15 percent aqueous solution Polyvinyl but ^ 'ral in one of polyvinyl alcohol Mixture of toluene and -

Isopropanol (7: 3)

4 15 percent solution of 15 percent solution of poly-polyvinyl butyral in a vinyl butyral in a mixture mixture of toluene and iso- of toluene and isopropanol propanol (7: 3) (7: 3).

The resins mentioned below are used instead of those in Table ■ I used resins mentioned for the primer layer liquid. Similar results are obtained.

Nos. 1 and 2 in Table I use sodium polyacrylate, dextrin, and polyvinylpyrrolidone, respectively.

In Wr. 3 and 4 in Table I is a rosin-modified phenolic resin, a xylene resin, polystyrene, an epoxy resin

309848/1002

or a petroleum resin is used.

The resins listed below are used in place of the resins shown in Table I for the topcoat liquid. Similar results will be obtained.

In No. 1 and 2 in Table I, sodium polyacrylate, polyvinylpyrrolidone, two paints of polyvinyl alcohol and the polyvinyl butyral resin or polystyrene are used.

In Nos. 3 and 4 in Table I, a xylene resin, a with Colophony-modified phenolic resin, polystyrene, an epoxy resin or a petroleum resin are used.

Example 12

When coating with the top layer liquid described in Examples 10 and 11, the dye can be dissolved in the solvent of the top layer liquid. This depends on the type of dye. Therefore, the paper color carrier can discolor the overlying color carrier when placed on top of one another. In this case, a first top layer with a 15 percent aqueous solution of polyvinyl alcohol is applied with an area coverage of 0.5 to 1.0 g / m ". After drying, a second top layer is applied with a 15 percent solution of polystyrene in a mixture of gasoline , Ligroin and toluene (3: 3: 4). With the help of these two coats, discoloration during coating can be prevented ^.:

3 0 9 8 4 8/1002

The shelf life and printing properties of the obtained Paper ink carriers are excellent.

Example 13

A 15 percent aqueous solution of polyvinyl alcohol is applied to paper with a basis weight of 55 g / m 2. After the primer layer has dried, a solution of 60 parts of Na ₂ Cr ₂ Oy in a 6 percent aqueous solution of the methyl cellulose used in Example 4 is coated. After thorough drying, a red color paste is applied in a pattern with a rotogravure printing machine. The red color paste is made from 120 parts of the ethyl cellulose used in Example 2, 100 parts of Aizen Cathilon Red 6BH (CI. 48020) and a mixture of 780 parts of xylene and butanol (8: 2) and thorough grinding in a ball mill. Finally, a 15 percent solution of a polyvinyl butyral resin in a mixture of toluene and isopropanol (7: 3) is applied to the color sample as a cover layer using a gravure printing machine. The area application is 1.2 g / m. A paper ink carrier is obtained which, when used according to Example 9, has good storage stability and good printing properties.

When using sodium acrylate, dextrin, an epoxy resin or a xylene resin instead of polyvinyl alcohol as a synthetic resin in the primer layer and when applying two Paints of polystyrene or polyvinyl alcohol and a polyvinyl butyral resin or polystyrene in place of the polyvinyl butyral resin in the top layer solution, paper ink carriers with a similarly good shelf life and good printing properties

30 9 848/1002

stocks received.

Example 14.

Example 13 is repeated, but initially to the Carrier applied the color pattern and then applied the layer containing the oxidizing agent. It will similar results as in Example 13 were obtained.

B e i s ρ i e 1 15

80 parts of crystal violet (CI. 42555) are dissolved in 1720 parts of water. Then carefully 200 parts of a. 20 percent aqueous solution of Na ₂ Cr ₂ 0γ was added. When the addition is complete, the solution is left to stand. The precipitate formed is filtered off, washed with water and dried

Share _,

net. 70 / of the oxidant treated crystal violet and 120 parts of the ethyl cellulose used in Example 2 are mixed together and placed in a ball mill carefully wed. A purple color paste is obtained,

On paper with a basis weight of 55 g / m 2, a 15 percent aqueous solution of polyvinyl alcohol applied. After the primer layer has dried, the purple color paste will appear imprinted according to pattern. Then the printed Sample with a 15 percent aqueous solution of polyvinyl alcohol coated. The area application is about 1.2 g / m 2 After the top layer has dried, a paper color carrier is obtained with good shelf life and good printing properties,

I. . ._- ■■■; - · ■; ■ ■

309848/1002

When using sodium acrylate. Dextrin, an epoxy resin or xylene resin instead of polyvinyl alcohol "as the resin component for the primer layer and when applying two coats made of polystyrene or polyvinyl alcohol and a polyvinyl butyral resin or polystyrene instead of polyvinyl alcohol A paper ink carrier with a similar shelf life and good shelf life is also obtained as the resin component in the top layer Printing properties. .

Example 16

50 parts of F ^ Ci ^ O- are in 950 parts of a 4 percent strength aqueous solution of the methyl cellulose used in Example 4 dissolved. This aqueous solution is based on lightweight, machine coated paper with a basis weight of

64 g / m 2 s perfect drying is achieved with a rotogravure printing machine.

64 g / m applied with a gravure printing machine so that a

100 parts of the ethyl cellulose used in Example 2 and 100 parts of Aizen Cathilon Red 6BH are mixed with 800 parts of a mixture of xylene and butanol (8: 2) and in grind carefully in a ball mill. You get a red one Printing paste applied in a pattern with a rotogravure printing machine the coated paper obtained is applied. This is followed by a gravure printing machine on the printed surface applied a 15 percent aqueous solution of polyvinyl alcohol. After perfect drying the top layer is obtained a paper ink carrier with good properties.

309848/1002

A similar paper color carrier is also obtained when using ■ application of polyvinyl butyral, polystyrene or two top coats of polyvinyl alcohol and polyvinyl butyral or polystyrene.

Example 17.

Example 16 is repeated, but the paint with the oxidizing agent is applied to the printed pattern. On that the top layer is applied. A paper color carrier is obtained with similar characteristics;

Example 18

(. CI 42555), 80 parts of crystal violet in 172O be ^- dissolved parts of water. Then 200 parts of a 20 percent strength aqueous solution of ilapCrpOy are carefully added. When the addition is complete, the mixture is left to stand. The precipitate formed is filtered off, washed with water and dried. 70 parts of the crystal violet treated with the oxidizing agent and 120 parts of the ethyl cellulose used in Example 2 are mixed with 810 parts of a mixture of xylene and butanol (8: 2) and the mixture is carefully ground in a ball mill. A purple coloring paste is obtained. The violet color paste is applied in a pattern to a lightweight, machine-coated paper with a basis weight of 64 g / m 2 using a rotogravure printing machine. A 15 percent aqueous solution of polyvinyl alcohol is then applied as a top layer using a gravure printing machine. A paper ink carrier with good properties is obtained.

309848/10 0 2

Example 19

Example 9 is repeated instead of the lightweight, however, machine-coated paper uses a laminated aluminum foil. There are color carriers with similar ones Properties preserved.

Example 20

The thermal transfer printing properties of those with the oxidizing agent treated basic dyes will match the printing properties of the basic dye compared.

The production of the color carriers using the basic dyes treated with the oxidizing agents is carried out according to Example 1, 2, 3 or 7. In a similar manner, color carriers are produced using the basic dye alone. _: tissue made from polyacrylonitrile fibers into contact and heated 75 seconds between heated plates to 19O ° C.

The hue obtained with the color carriers of the invention isL considerably deeper, purer and more even than the one with de: ·; basic dye 'hue obtained without oxidizing agent. The results are summarized below.

'ORIGINAL INSPEOTBO "3 09848/1002"

(a) Aizen Cathilon Blue 5G (CI. 51005)

Oxidizing agent producing the color density state of the ge ™

Color vehicle colored fabric

Sodium permanga-
nat example 7th e 1.30 Well anhydrous
Barium peroxi d example 7th f 1.32 Well Sodium bi Ehromat example 3 - 1.26 Well none - 0.40 bad, un
evenly.

(b) Aizen Cathilon Red 6BH (CI. 48020)

Oxidizing agent Manufacture of the color density State of the

Color vehicle colored n fabric

anhydrous Baisprel 7 f 1.20 good rium peroxide.

Sodium dichromate Example 2 1.36 good

none '- 0.50 ⁱ bad, un

evenly

(c) Malachite green (CI. 42000)

Oxidizing agent producing the color density state of the ge ~

Dyes colored fabric;

Sodium permanga- ■
nat example 7th e 1.20 Well anhydrous Ba
rium peroxide example 7th f. 1.14 Well Sodium dichromate example 1 1.12 Well Potassium dichromate example 7th d 1.26 Well none ■ 0.60 bad, un
evenly.

The color density was measured with a Macbeth densitometer type RD 100 determined.

3 09 848/10 02

A sample of the paper color carrier, which only contained the basic dye (Aizen Cathilon Blue 5B), is used with brought into contact with the polyacrylonitrile fabric and heated to 210 ° C. between heating plates for 75 seconds. The printed The fabric had inferior properties than the fabric treated with a paper dye carrier of the invention in which the basic dye had been treated with the oxidizing agent. The tissue density of the former is less than that of the fabric dyed according to the invention. The uneven coloring could not be achieved even when the heating temperature was increased be improved. The color of the fabric turned yellow.

Example 21

Using paper color carriers prepared according to Example 1 · fabrics made of nylon, silk and wave according to colored using the thermal transfer printing process.

Table II Aizen
Cathilon
Red 6BH Aizen
Cathilon
Blue 5G dye Aizen
Cathilon
Blue 5G 190 ⁰ C
45 see .190 ⁰ C
60 sec Printing conditions 17O ⁰ C
60 sec 0.3 mm
Tissue in
Twill
manure 1.0 mm
Tissue in
canvas
bond. tissue 0.3 mm
Nylon fabric in
Canvas bin
manure Red blue Hue of ge
colored fabric blue

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Example 22

The grapes printed according to Example 8 by the thermal transfer printing process are treated with steam. In this way the paint is completely fixed on the substrate ₍ and purer shades are obtained. The results are summarized in Table IU.

Table III Blue 5G Damper edinpun ^ '. m tissue dye Blue 5G 105 ° C 5 min Polyacrylni tri1 Aiζen Cathilon Red 6BII 110 ⁰ C 3 min polyamide Aiζen Cathilon Blue 5G 110 ⁰ C 10 min " silk Aiζen Cathilon HO ⁰ C 15 minutes Wool Aizen Cathilon

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Claims (20)

Claims 1 .. y color carrier for the thermal transfer printing process, consisting a support on which a pattern of a basic dye with poor heat transferability, an oxidizing agent to increase the transferability of the basic Dye in the heat and a binder is applied. 2. Ink carrier according to claim 1, characterized in that day Pattern of an underlayer of the basic dye and the binder and an upper layer of the oxidizing agent and the binder. 3. Ink carrier according to claim 1, characterized in that da.s Pattern of an underlayer of the oxidizing agent and the binder and an upper layer of the basic dye and the binder. 4. Ink carrier according to claim 1, characterized in that the carrier paper, finished paper; Cellulose, foil or sheet material made of a heat-resistant polymer, foil or sheet material made of a metal or laminated metal foil is. 5. Ink carrier according to claim 1, characterized in that "the basic dye a basic methine dye (cyanine dyes ) or cationic dye, a basic diphenylmethine dye or cationic dye, a basic triphenylmethane dye or cationic dye, eii> basic 309848/1 002 shear xanthene dye or cationic dye, a basic one Acridine dye or a cationic dye, a basic quinone imine dye or a cationic dye, a basic one Is anthraquinone dye or a cationic dye with quaternary ammonium groups. * 6. ink carrier according to claim 5 ,. characterized in that the basic dye Aizen Cathilon Yellow. 3GLH (CI. 48055), Aizen Cathilon Red 6BH (CI.48020), Malachite Green (CI.'42000), Crystal Violet (CI.42555), Aizen'Cathilon Blue 5G- (CI. 51005), Aizen Basic Cyanine 6GH (CI. 42025), Aizen. ■■ ■ Methylene Blue FZ (CI. 52015), Aizen Cathilon Brilliant Yellow 5GLH (CI. Basic yellow 13), Aizen Cathilon Orange-RH (CI. 48040) or Astrazon pink FG (CI. 48015). 7. color carrier according to claim 1, characterized in that the oxidizing agent permanganic acid _s sodium permanganate, potassium permanganate, chromic acid, sodium chromate, potassium chromate, ammonium chromate, sodium dichromate, potassium dichromate, ammonium dichromate, magnesium chromate, calcium chromate, potassium chlorochromate, chromyl chloride, hydrogen peroxide, sodium, or calcium peroxide , Sodium, potassium or ammonium nitrate. 8. ink carrier according to claim 1, characterized in that the Binders methyl cellulose, ethyl cellulose, carboxymethyl cellulose, Cellulose acetate, cellulose butyrate, sodium alginate or its derivative, polyvinyl alcohol, polyvinyl butyral Acrylic resin, polyvinylpyrrolidone, polyvinyl methyl ether, starch, gum arabic, tragacanth. or gelatin. 309848/10 02 9. Ink carrier according to claim 1, characterized in that a cover layer made of a synthetic resin film is applied to the pattern through which the basic dye cannot pass under normal conditions. . 10. Ink carrier according to claim 9, characterized in that the Synthetic resin of the top layer made of a water-soluble resin, in particular polyvinyl alcohol, sodium acrylate or polyvinylpyrrolidone, or an oil-soluble resin, in particular a xylene resin, a phenolic resin modified with Colophoriium, polyvinyl butyral, an epoxy resin, polystyrene or a petroleum resin. 11. Ink carrier according to claim 9, characterized in that the cover layer consists of at least two layers of different Synthetic resins. 12. Ink carrier according to claim 1, characterized in that the carrier is coated with a primer layer through which the basic dye cannot pass under normal conditions. 13 · Ink carrier according to claim 1, characterized in that the Support with a primer layer and the pattern is coated with a top layer, by means of which the basic dye cannot pass under normal conditions. 14. Process for thermal transfer printing of print media, in particular Textile flat structures, characterized in that a color carrier, which consists of a carrier, is on which a 309848/1002 Basic dye pattern with poor transferability in the heat, an oxidizing agent, to increase the ' Transferability of the basic dye in heat and a Binder is applied, brings on its pattern side with the print carrier in contact, the structure is heated under pressure and then removed the ink sheet from the print carrier. 15. The method according to claim 14, characterized in that the print carrier, textile fabrics made of natural fibers, such as Cotton, wool and silk, cellulose acetate, a polyamide, polyacrylonitrile or polyvinyl chloride, or film or sheet material made of a polyamide, polyacrylonitrile or polyvinyl chloride is used. 16. The method according to claim 14, characterized in that the heating is carried out at temperatures of about 80 to 250 ⁰ C. · 17. The method according to claim 14, characterized in that the heating is carried out at pressures of about 50 g / cm to 20 kg / cm. ■ 18. The method according to claim 14, characterized in that the heating is carried out for about 30 to 90 seconds. 19. The method according to claim 14, characterized in that a color carrier is used, on the carrier _{v of which} a color layer of the basic dye, the oxidizing agent and the binder is applied to the entire surface, 309848/1002 and on which a mask is laminated which does not print Covers areas and leaves printing areas free. 20. The method according to claim 14, characterized in that an ink carrier is used which consists of a carrier, on which a pattern on the basic dye, the oxidizing agent and the binder is applied, and on the Pattern has a top layer made of a synthetic resin, through which the basic dye does not under normal conditions can pass through. 309848/1 Ό U 2