EP0020292A1 - Auxiliary supports for transfer printing and thermographic printing process using these supports - Google Patents

Abstract

Auxiliary dry thermoprinting supports consisting of flexible bands stable to heat, generally made of porous or perforated paper and bearing dyes of low volatility.

Description

The present invention relates to new auxiliary supports for transfer printing, also known as dry printing or gas-phase thermal printing.

The auxiliary supports used in dry transfer printing are generally sheets or strips of paper which carry the dye (s) which are transferred hot to the material to be printed. For the printing of thick materials such as velvet, carpets, blankets or rugs, the required penetration of the dyes into the material to be dyed or printed is obtained, either by using auxiliary supports carrying so-called "penetrating" dyes. that is to say dyes which already below 180 C sublimate or vaporize more than 50% in less than 25 seconds, either by carrying out the transfer operation under reduced pressure. Porous transfer supports have also been used to increase the penetration of sublimable dyes into the dyeing material, through which a current of hot air is passed during the transfer (see German patent application). 26 28 676 and French patents 21 14 925, 22 47 356 and 22 60 452). These porous or perforated substrates do not allow regular printing of large areas, probably because of the inconsistent texture of the porous papers used.

In German patent application 27 40 137, the surface perforation of the printed face of auxiliary supports is described during their passage through a vacuum transfer calender to allow better elimination of the moisture present in these supports. This kind of incomplete perforation and of variable dimensions does not make it possible to obtain auxiliary supports usable in the transfer process in which a current of hot air entrains the product or products to be transferred. On the other hand, the papers claimed and described in German application 28 15 864 from the company known as Armstrong Cork Corporation can be used in this technique, their only drawback being that on very thick materials the intensity of the print leaves something to be desired: when the penetration is sufficient, the intensity is too low and when the quantity of air is reduced to have sufficient intensity, it is the penetration which no longer is.

The supports of the present invention overcome the drawbacks of known auxiliary supports and also have the advantage of extending the range of supports available and the scope of the transfer technique. In fact, the supports of the present invention allow the transfer operation to be carried out on materials on which only satisfactory results were obtained with the known supports.

• a) la porosité ou la perforation de la base du support est régulière et sa perméabilité à l'air est de 50 à 500 litres par seconde et par mètre carré sous une pression de 98,1 Pa (1 g/cm²) et
• b) le ou les colorants formant le motif à transférer sont retenus sur la base perforée par un liant, ils se volatilisent sans décomposition notable à une température inférieure à 320°C et leur volatilité est plus faible que celle des moins volatils parmi les colorants utilisés dans le procédé classique de transfert en phase gazeuse.

The auxiliary supports of the present invention bear on one side of a flat, flexible and heat stable base, preferably on one side of a sheet or strip of porous or perforated paper, one or more zones colored having at least 0.2 g / m of dyes which under the action of heat pass to the state of vapor without significant decomposition. They are characterized by the following two points:

• a) the porosity or the perforation of the base of the support is regular and its air permeability is 50 to 500 liters per second and per square meter under a pressure of 98.1 Pa (1 g / cm ² ) and
• b) the dye (s) forming the pattern to be transferred are retained on the base perforated by a binder, they volatilize without significant decomposition at a temperature below 320 ° C and their volatility is lower than that of the less volatile dyes used in the conventional gas phase transfer process.

In what follows the temperatures are indicated in degrees Celsius; the term "polyester" refers to films or sheets or fibers of poly (ethylene terephthalate).

To prepare the new auxiliary supports of the present invention, papers are printed whose porosity is such that, under a pressure of 98.1 Pa (that is to say under a pressure of 1 g per cm ² ), they allow between 50 and 500, preferably 100 to 300 liters of air per second and per square meter.

By porous paper is meant both papers in the literal sense of the term as thin felts or nonwovens of cellulosic fibers, or perforated papers. It is also possible, by any desired method, to print sheets or strips of cellophane, of aluminum or of little or not porous paper (which are easier to print than porous papers). The printing is done before or after perforation with aqueous or solvent printing inks which contain a binder (see French patents 1 223 330 and 1 575 069 for example) and one or more coloring matters free from strongly acid groups such as sulfonic groups. The binder serves both to disperse dye in the ink and to thicken the ink; it will also retain the dye on the printed side of the support. These binders are well known to those skilled in the art, as are printing methods. To prepare the supports of the present invention which must bear colored areas of at least 0.2 and preferably at least 0.4 g of dye per m, it is necessary, it goes without saying, to ensure that the ink contains enough dye; in general, inks containing 0.2 to 20% dye are used and enough ink is printed to have the desired amount of ink per _m ² . It is advantageous to use an ink quantity that is larger the thicker the material to be thermo-printed with the support. Thus, for materials more than 1 mm thick, supports are used, depending on the desired penetration, the patterns to be transferred can contain up to 1.6 and even 2 g of ink per m ² . The porous papers of the present invention are printed like the papers little or not porous, but it is then advantageous to use more concentrated inks or else to coat in surface the porous papers with a smooth layer which facilitates their printing.

It goes without saying that the papers of the present invention must be heat stable and they must have sufficient tensile and tear strength so that they can be printed and used in a machine for continuous transfer in which air at a temperature of up to 260 ⁰ is pressed through the printed paper and the material to be dyed (printed). Preferably, strips of paper at least 1 m wide and several tens or even several hundred meters long are used, for example, the papers indicated in German patent application 28 15 864, which are printed as indicated above.

Once printed, the substrates with little or no porosity must be perforated so that, under a pressure of 98.1 Pa (that is to say under a pressure of 1 g per cm2), they allow between 50 and 500, preferably 100 to 300 liters of air per second per square meter. The perforation can be done in a manner known per se, for example, by means of a laser, by electrical discharge or mechanically. Thus it is possible to mechanically perforate sheets of paper or strips of paper which are not very porous or not porous and which are entrained between at least one rotating roller having peripherally and radially a multiplicity of projecting points, and at least one rotating roller ensuring the counter-support. necessary for the puncturing action of the tips without damaging them. The protruding points can have any desired section: oval, round, square, rectangular or even triangular or houndstooth. They are preferably cylindrical and ensure a regular perforation right through, c ^t is to say that each has substantially the same section perforation along its entire length and that the perforations are distributed over the colored surface of the support according to the invention so that in each surface unit there are the same number of perforations of the same section, These are preferably of a diameter less than 80 micrometers and spaced from each other by 100 to 200 micrometers, the total area of the perforations not exceeding 10% of the total area of the colored area.

Instead of a roller with fixed protruding points, it is also possible to perform the perforation using mobile needles or by any other means ensuring regular perforation of the base of the support (laser, electric shocks, etc.).

As mentioned above, the printed supports of the present invention make it possible to dye and deeply print thick materials (carpet, velvet, etc.) without having to use so-called "penetrating" dyes, that is to say ie using less volatile dyes than those used in the conventional thermo-printing process (35 seconds at 210 ^° ); these coloring matters pass into the vapor state below 310 ° but cannot be used in this process due to their too low volatility. These coloring matters are generally of the type of so-called dispersion dyes, vat dyes or pigments. They may be indigoldes, especially thioindigoldes, azo dyes with a molecular weight between 340 and 600, preferably those which derive from arylides of B-hydroxynaphthoic or acetylacetic or even benzoylacetic acid and which have a weight molecular at least 400, anthraquinonics also with a molecular weight between 340 and 600 or even disazo dyes, styrylic derivatives, etc. According to the invention, it is necessary to choose dyes which sublimate or vaporize below 310 ° without significant decomposition and which have less volatility than the least volatile among the dyes generally used in printing by transfer in gas phase. These are dyes which, when transferred in 35 seconds to polyester under atmospheric pressure or to cotton impregnated with 8 - 10% polyethylene glycol, reach their maximum intensity only above 225 °, that is to say say dyes which, on transfer, give, due to their lower volatility, less intense prints than yellow hydroxyquinophthalone and brominated hydroxyquinophthalone, red 1-amino-2-phenoxy- (or 2-hydroxyethoxy-) 4-hydroxy-anthraquinone and blue 1-amino-2-cyano -4-anilino anthraquinone and brominated diaminoanthrarufin which are with the yellow 0 - (4 ^t -acetaminophenylazo) -p-cresol, the red l-amino-2-methoxy-4-hydroxy-anthraquinone and the blue 1,4-dimethylomino- anthraquinone, the most commonly used dyes in conventional gas-phase transfer printing.

A simple method for assessing the volatility of sublimable dyes consists in printing a paper with an ink containing the dye that is to be tested, so as to have approximately lg of dye per m ² of the transfer paper thus obtained, then to transfer to 205 ° in 35 seconds on a stack of 10 polyester fabrics each weighing 60g per m ² and having per cm ² ₁ 46 warp threads of 8.5 tex and 43 weft threads of 5.8 tex (tex = g per Km ); the number of colored fabrics indicates the volatility of the dye. Thus, the conventional dyes used in dry transfer are visible, in this test, on 3 to 9 fabrics stacked one on the other, while the dyes to be used according to the present invention are only on the fabric closest to the transfer paper or the two closest.

Dyes which transfer without significant decomposition below 310 ° and which reach their maximum intensity at transfer under atmospheric pressure, above 225 ° (maximum of the transfer curve) fulfill the most important condition for use in the present invention.

By way of example of dyes of this kind, one can mention: 1- (p-toluene-sulfonylamino) -4-hydroxyanthraquinone, l- (p-phenylbenzoylamino) -anthraquinone, 1-amino-2-methoxy-4 -benzoylamino-anthraquinone, its methyl- or methoxy-benzoyl- derivatives, 1,4 and 1,5-diphenylamino-anthraquinones and their derivatives carrying one or more methyl groups the, one or more chlorine, fluorine or bromine atoms, or even one or more trifluormethyl groups, indanthrene, benzoylamino-isothiazolanthrone 1-amino-4-hydroxy-2- (B-phenoxycarbonyloxy-ethyloxy) -anthraquinone, the B-methoxy-propyl-or-ethylimide of 1,4-diamino-anthraquinone-2,3-dicarboxylic acid, the benzyl- or phenyl-ethylimide of the same acid, the alkylamides and the phenylamides of the acids 1-phenylazo-2-hydroxy-3-naphthoiques which bear on one or the other or on the two phenyl radicals one or more substituents chosen from the group consisting of fluorine, chlorine or bromine atoms, groups methyl, ethyl, isopropyl, methoxy, ethoxy, trifluormethyl, NO ₂ , acrylamino, sulfonamide, methanesulfonyl and CH ₃ -CO-; reds 50, 54, 72, 82, 115 and 117, yellows 85, 65, 56 and 53, oranges 80 and 125, purples 64 and 57, green 7, blues 191, 165, 153, 95 and 87 of the class of disperse dyes of the Color Index published by The Society of Dyers and Colourists, tetrachloro and tetrabromindigo, dichloro-dimethylthioindigo, dichlorindigo, diethoxy- and diethyl-mercaptothioindi- go, the condensation product of acenaphthenequinone on 3-thianaphthenone (thioindoxyl) and its brominated derivative, dibenzopyrenequinone, the anthanthrone and its chlorinated and brominated derivatives, 1-isopropylamino-4 (p ^t- phenoxyanilino) anthre- quinone, 1-isopropylamino-4- (m'-phenylsulfonylamino-anilino) -anthraquinone, 1-isopropylamino-4- (m'-phenylsulfonylaminoanilino) -anthraquinone, 1-isopropylamino-4- (m'- dimethylamino-sulfonylanilino ) -anthraquinone, 1-benzoylamino-4- (p ^t- isopropyl- or isoamylanilino) -anthraquinone, the mono-azo dye obtained by coupling diazotized nitraninine or mitrotoluidine, on barbituric acid or on naphtanilide of acetylacetic or benzoylacetic acid, the dioxazines obtained by cyclizing the condensation products of chloranil (tetrachloro-p-benzoquinone) on the naphthylamine , aminopyrene and aniline and its derivatives such as p-chloraniline, toluidine, anisidine, cresidine, p-isopropylaniline, m-trifluormethylaniline, p-dimethylamino-aniline finally the dyes obtained by coupling of o-nitro-p-methyl or p-methoxy-aniline diazotized on barbituric acid or on the naphthhanilide of benzoyl-acetic acid or that obtained by coupling of the nitrophenylaniline diazotized on the naphthhanilide of acetylacetic acid as well as the coupling product of 2-chloro-5-methoxy-aniline diazotized on the morpholide of the acid 2-hydroxy-3-naphtholque.

With the above low volatility dyes, supports according to the present invention are obtained which are particularly advantageous when aqueous or solvent inks are used for printing the porous (or perforating) papers indicated above, which also contain at least 10%, preferably 25 to 75%, of a more volatile dye which transfers in the vapor phase at 200 ° under atmospheric pressure and which reaches the maximum of its transfer curve between 205 ⁰ and 220 ⁰ in 35 seconds of transfer at this temperature. The use of more volatile dyes, for example those which in 35 seconds of transfer at atmospheric pressure reach the maximum of their transfer curve already below 205 should be avoided, because they give supports of little interest, the dyes of this type passing through all the material to be dyed or printed and sometimes even causing pollution of the equipment used.

The dyes to be used to prepare the auxiliary supports of the present invention are for the most part known. They are found commercially among the dyes in the Dybln ranges from Du Pont, Cellestren by BASF, Terasil-X by Ciba-Geigy and in the corresponding ranges by other manufacturers of dyes (Sandoz, ICI, Bayer, etc.).

As indicated, auxiliary supports are obtained which can carry a single layer of dye or patterns of several colors. In the latter case, much better results are obtained when not left empty (ie not printed) the white parts of the drawing, but that one prints them using a colorless ink of the type of the colored inks used to print the drawing itself.

In the following nonlimiting examples, the parts and percentages indicated are understood, unless otherwise stated, by weight and the temperatures in degrees Celsius.

Example 1

• 40 parties de LYOPRINT TPA (Ciba-Geigy)
• 15 parties de UIBATEX S (Ciba-Geigy)
• 12 parties d'ALBEGAL FFD (Ciba-Geigy) en solution aqueuse à 10% et
• 25 parties d'eau et
• 5 parties d'éther de pétrole.

A pattern is printed on the rotary frame on a base paper formed by a sheet of cellulosic fibers. This paper with a weight of 70 g / m and a permeability of 23 m ³ / minute (type VL 200 from JC Binzer, Hatzfeld / Eder RFA) is printed at a rate of 20 g of dry matter per square meter at using the printing ink in the frame obtained by mixing 7 parts of 1-amino-2-phenoxy-4-hydroxyanthraquinone and 3 parts of 1-amino-2-ethoxy-4-hydroxy-anthraquinone, the ethoxy residue carries in position B a substituent of formula -O-CO-OC ₆ H ₅ , in 90 parts of the mixture formed by:

• 40 parts of LYOPRINT TPA (Ciba-Geigy)
• 15 parts of UIBATEX S (Ciba-Geigy)
• 12 parts of ALBEGAL FFD (Ciba-Geigy) in 10% aqueous solution and
• 25 parts of water and
• 5 parts of petroleum ether.

Once dry, the paper thus obtained can be used to print by transfer a red pattern on a polyester velvet for example on a velvet with a pile height of 2mm such as that of the house Viscosuisse (type 110 f 23 x 1HE) which weighs 260 g / m ² . For this purpose, transfer to an air flow of 35 m ³ / h for an area of 576 cm ² . In the sandwich formed by the paper and the pile the pressure drop of 1.1 g / m ² on the surface of the pile. The air temperature is 235 ° and that on the surface of the material to be im primer is 215 °, thus obtaining a solid red impression in the light and good penetration.

Porosity measurement on a Frazier porosimeter

An air flow (X) is sucked through a filter paper of given section and under a constant vacuum (2.5 mm H ₂ 0). An amount of air is therefore measured, unlike the pressure drop where a vacuum is determined according to a given flow rate. The air volume (X) is reduced to a unit of time for a given surface (929 cm ² ) and is expressed in CFM (cubic feet minute).

The porosity of Binzer VL 200 paper measured in this way is 76 CFM, that is to say 2.15 m ³ / min.

Instead of Binzer paper, papers with a permeability less than half but more resistant to traction and better calendered are used in the same way. Auxiliary supports are also obtained which are very suitable for thermal printing in an air stream.

Example 2

The operation indicated in Example 1 is repeated, but using only the dye 1-amino-2-ethoxy-4-hydroxyanthraquinone which carries in position B of the ethoxy residue the substituent of formula -0-CO- 0-C ₆ H ₅ . The velvet is printed under the conditions indicated. A lighter shade is obtained than in Example 1, but more solid in light.

Example 3

• encre violette) : l-p-toluènesulfonylamino-4-hydroxy-anthraquinone.
• encre jaune ) produit de copulation de l'acide barbiturique sur la nitro-anisidine diazotée.
• encre bleue ) : B-méthoxyéthylimide de l'acide 1,4-di- amino-anthraquinone-2,3-dicarboxylique.
• encre rouge ) : colorant de l'exemple 2.
• encre incolore ) : même encre qu'à l'exemple 1 mais sans colorant.

On paper with an air permeability of 80m ³ / min. per square meter under 1 mbar of pressure, a multicolored pattern is printed on the rotary frame using inks containing the following colors:

• purple ink): lp-toluènesulfonylamino-4-hydroxy-anthraquinone.
• yellow ink) product of copulation of barbituric acid on diazotized nitro-anisidine.
• blue ink): B-methoxyethylimide of 1,4-di-amino-anthraquinone-2,3-dicarboxylic acid.
• red ink): dye from Example 2.
• colorless ink): same ink as in Example 1 but without colorant.

• On applique le support auxilfaire sur un velours de polyester dont la hauteur du poil est de 6mm et on fait passer à travers le papier et le velours un courant d'air chauffé à 230° à raison de 54 m³/h pour une surface de 576 cm², la pression du papier sur le velours étant au cours de cet essai d'environ 1,6 g/m². On obtient ainsi un velours imprimé en profondeur dont les teintes sont très solides à la lumière.

After drying, an auxiliary thermo-printing support is obtained which lends itself well to transfer into a current of hot air, for example as follows:

• The auxiliary support is applied to a polyester velvet whose pile height is 6mm and a stream of air heated to 230 ° is passed through the paper and the velvet at a rate of 54 m ³ / h for a surface area of 576 cm ² , the pressure of the paper on the pile being during this test approximately 1.6 g / m ² . We thus obtain a deep printed velvet whose colors are very solid in the light.

Example 4

• colorant de l'encre rouge : produit de copulation du morpholide de l'acide B-hydroxynaphthoique sur l'o-méthoxy- p-chloràniline diazotée ;
• colorant de l'encre bleue : 1-benzoylamino-4-(p-butyl anilino-) anthraquinone ;
• colorant à l'encre verte : mélange à parties égales du colorant de l'encre bleue ci-dessus et du produit de copulation du naphtylamide de l'acide benzoyl- ou acétylacétique et de la nitrotoluidine diazotée.

A pattern of several colors is printed on the flat frame on a paper with an air permeability of 110 liters per second and per square meter, using the inks obtained by mixing 10 parts of each of the following dyes with 90 parts of the mixture. thickeners and water indicated in Example 1.

• red ink dye: coupling product of the morpholide of B-hydroxynaphthoic acid on diazotized o-methoxy-p-chloraniline;
• blue ink dye: 1-benzoylamino-4- (p-butyl anilino-) anthraquinone;
• dye with green ink: mixture of equal parts of the dye of the blue ink above and the copu product Benzoyl- or acetylacetic acid naphthylamide and diazotized nitrotoluidine.

• On foularde un velours de coton ayant une hauteur de poil d'environ 2 mm (par exemple celui de la maison dite Mecha- nische Seidenueberei AG, Viersen RFA) avec une solution aqueuse à 10% de polyéthylène-glycol d'un poids moléculaire de 400. On exprime à environ 100% de prise de bain, et sèche à 10 minutes à 120°. On applique sur le velours ainsi traité le support auxiliaire ci-dessus, face imprimée contre le velours et on fait passer pendant 25 secondes à travers le papier et le velours un courant d'air chauffé à 250°, à raison de 35 m³/h et une pression de 0,9 g/m² du papier sur le velours qui est ainsi porté à 230°. On obtient une impression en profondeur qu'on peut laver 10 minutes avec de l'eau à 60°. Après séchage, l'impression peut être traitée à l'aide de résines d'apprêt. Avant ce traitement, l'impression est déjà très solide aux traitements par voie humide et à la lumière.

The white parts of the pattern are printed with the mixture of thickeners containing no dye as if it were a colored ink. After drying, an auxiliary thermo-printing support is obtained making it possible to print cotton or polyester cotton by transfer into a stream of hot air, for example in the following manner:

• A cotton velvet having a pile height of about 2 mm (for example that of the house called Mecanische Seidenueberei AG, Viersen RFA) is fouled with a 10% aqueous solution of polyethylene glycol with a molecular weight of 400. It is expressed at about 100% bathing, and dried at 10 minutes at 120 °. The above auxiliary support is applied to the velvet thus treated, printed side against the velvet, and a stream of air heated to 250 ° is passed for 25 seconds at a rate of 35 m ³ / h and a pressure of 0.9 g / m ² of the paper on the pile which is thus brought to 230 °. A deep impression is obtained which can be washed for 10 minutes with water at 60 °. After drying, the print can be treated with primer resins. Before this treatment, the impression is already very solid with wet and light treatments.

Example 5

A pattern is printed on the rotary frame on a paper having a porosity of 26 CFM, i.e. 130 l / sec.m ² (type 2018 from the house of ARJOMARI) using a red ink containing the dye 1-amino-2-methoxy-4-benzoylamino-anthraquinone, the white parts of the motif being printed with a "white" ink containing a mixture of thickeners and, instead of coloring, an optical whitening agent of the kind of those indi ques to French patent 157 4528.

After drying, an auxiliary thermo-printing support is obtained, making it possible to print polyester velvet or polyester-cotton in a stream of hot air, for example as follows: the printed side of the support is applied to the velvet. A stream of air heated to 240 ° is passed for 30 seconds through the paper and the pile, at a rate of about 35 m ³ / h under a pressure of 0.9 g / _m ² from the paper to the pile. reaches a surface temperature of around 216 °. This gives a solid impression and very good penetration.

Claims (11)

1. Auxiliary supports for transfer printing which bear on one side of a flat, flexible and heat stable base, preferably on one side of a sheet or strip of porous or perforated paper , one or more colored zones having at least 0.2 g / m ² of dyes which, under the action of heat, pass into the vapor state without significant decomposition, characterized in that a) the porosity or the perforation of the base of the support is regular and such that at 205 ° C it allows between 50 and 500 liters of air per second and per square meter to pass under a pressure of 96.1 Pa (1 g / cm ² ) and b) the dye (s) forming the pattern to be transferred are retained on the base of the support by a binder, volatilize without significant decomposition at a temperature below 310 and their volatility is lower than that of the less volatile dyes generally used in conventional gas phase transfer printing. 2. Supports according to claim 1, characterized in that they carry dyes which, under atmospheric pressure, reach the maximum of their transfer curve at a temperature above 225 ° C. 3. Supports according to claim 1, characterized in that the holes drilled in the base of the support are elliptical or round and of a diameter not exceeding 80 micrometers, preferably with a diameter of 0.01 to 0 0.05 mm or smaller. 4. Supports according to claim 1, characterized in that the base of the support is one in. homogeneous roughness and such that, under a pressure of approximately 1 mbar, it lets through 100 to 300 liters of air per m ² and per second. 5. Supports according to claim 1, characterized in that the base of the support carries a colored pattern which includes dyes which are too low in volatility to be able to be used in conventional transfer printing and the white parts of which are printed using an ink whose thickener does not contain a sublimable dye but possibly a sublimable optical brightening agent. 6. Supports according to any one of the preceding claims, characterized in that the dyes forming the pattern to be transferred have different volatilities, each color comprising at least one dye which can be used in transfer printing in the gas phase under atmospheric pressure and a dye of identical or at least similar color but clearly less volatile. 7. Supports according to any one of the preceding claims, characterized in that they carry dyes forming a pattern to be transferred, dyes which have at least part of them a molecular weight greater than 340 and a group -CO -NH-. 8. Supports according to any one of the preceding claims, characterized in that the colors to be transferred are formed by mixtures of dyes of similar shades but of different volatilities, the proposal for the dye that is not very volatile in the mixture being at least 25% and preferably at least 40%. 9. Supports according to claim 8, characterized in that they consist of strips of printed paper at least 1.2 m wide. 10. Supports according to claim 8, characterized in that at least one of the most volatile dyes of the mixtures of claim 8 is chosen from the following dyes: o- (p'-acetaminophenylazo) -p-cre-sol, 4- (o'-nitro-p 'methylphenylazo) -3-methyl-5-pyrazolone, hydroxyquinophthalone and its brominated derivative, 2-methoxy- or 2 phenoxy-1-amino-4-hydroxyanthraquinone, 1,4-dimethyl- or dibutylaminoanthraquinone, 1-amino-4-anilinoanthraquinone, 1-amino-2-cyano-4-ethylamino- or 4-anilino-anthraquinone, 1-tolylamino-4-hydroxy-anthraquinone, 1,5-dihydroxy-4-amino-8 -isopropylaminoanthraquinone. 11, thermo-impression process, characterized in that a stream of air heated to 220-260 ° C is passed through the assembly consisting of a support according to one of claims 1 to 9, the printed side of which is applied to the material to be printed.