Process of impression per transfer of fibres of cellulose or mixed fabrics containing of fibres of cellulose and supports auxilaires for the implementation of this process.
A transfer printing method of cellulose fibers or blended fabrics containing such fibers, using auxiliary supports, the method characterized by the fact that impregnates the fabric moistened with water by compounds serving as both a solvent for the dyes transfer and crosslinkers potentials for cellulose, drying the fabric and prints it, by the transfer printing process, with sublimable dyes or optical brighteners, in the presence of a catalyst cross-links the applied to an auxiliary support. The cotton is generally dyed or printed with reactive or vat dyes; the use of dispersed dyes cannot be contemplated since these dyes do not affinity for cellulose. For transfer printing whose principle is described, for example, in French Patent № 1,223 330 or the German Patent № 1,769 757, dyes are needed which sublimate in a temperature range between 160 and 220 °c in passing then of the auxiliary carrier to the substrate. Dyes of this type are mostly found among the disperse dyes which, just as the e., does not however have affinity for cellulose. The new method allows, in a simple, secure the sublimation dyes being permanently in or on cellulose. This is effected by the attachment using auxiliary agents forming both solvents for the dye and the crosslinkers potentials for cellulose. As auxiliary agents of this type it is will indicate, for example, derivatives of urea or melamine-di - or polyfunctional etherified, carrying methylol groups. Are particularly suitable, ethyl ether, propyl or butyl, but above all the methyl ethers. The auxiliary agents must wear methylol groups at least two, preferably more than two groups. The melamine derivatives are therefore preferably used. Examples of suitable auxiliary agents, it will indicate the following groups of compounds: nhch2 gold NHCH-TO-ÛR ζ Ν ^ hC2 gold CH THE QR ROH_C 1/NR 1 ^ ^ R. (OHjC) (HM2 0)the nR 2! 2 j. 0 5} R0CH2 ^ ^ - HM - K.2 0R THE II Z0 ' - RGCE " - HINDERED N-CH GOLD L_ ^ J IS2 RR / SPEE C-N-N-CH-GOLD 2, 1 , Ir2 0 therein1 ' - ROSH-A-N-N-CH-GOLD 2 ·ν 2 A RO C-N, "(HM 20) the nR ROSH 2.0 * ^Œ 2°R or, n-c-0 (the Chl CHL and 0) to c-n-. , R.WITH (OSH,)"V. (HMthe O 0) R. in which formulae ζ η 2 η η is O or 1, R is an alkyl group to R1 is 1' hydrogen or a radical R, 2 R is a radical of the formula - (CH CH-.0) The R, and 2, 2 m. m is a number ranging from 1 to 20. n denotes the number 1 and preferably m represents advantageously 1, 2 or 3. As particularly preferred exceptions include, for example, NlCHjOCHjJj I (HM2 0CB3)3 to 5 THE N (HM2 OSH3 )2 or In a particularly advantageous embodiment, it is desirable that a melamine derivatives are indicated above in conjunction with carbamate characterized by the above formulas wherein R is preferably a methyl group and m 1, 2 or 3. May also be used advantageously, in combination with melamine compounds, carbamates unsubstituted on the nitrogen; a combination with the other compounds stated above is also possible. May be employed in conjunction with other auxiliary affecting, for example, on the feel of a good dye uptake. By way of example, it will indicate the products of ethoxylation and the polymers indicated, for example, in German patent no. 2,458 660. As catalysts which triggers the cross-linking, exceptions include especially substances acids or potentially acids such as those used for the finishing of noble cellulose, thus acids, halides or metal nitrate or ammonium salts. As an example, it will indicate the magnesium chlorides, ammonium, tributyl ammonium or triethanolammonium, hydrochloride 1.3-to-diaminopropanol, ammonium nitrate, zinc nitrate or ammonium rhodanide, as well as maleic acid, citric acid, tartaric acid, fumaric acid. Among preferred catalysts at industrially, it will indicate the NH ^ LC, MgCl2 , maleic acid, the NH ^ ^ no. of Zn (n03 )2 # AndMrepresents ZnCl2 or Mg (n03 )2 . As sublimation dyes exceptions include, for example, known colorants by the German patents № 1,769 757, 1,771 813, 1,771 812, 2,309 131 or 2,300 487. More specifically, it will indicate the following dyes: THE C.I. 11,855, 58,900, 11,110, 60,755, 62,015, 61,505, 61,100, 61,105. Suitable optical brighteners are known, for example by the German Patent № 1,769 761. The novel process is advantageously carried out by treating the fabric containing cellulose fibers with an aqueous liquor containing the auxiliary agent. The concentration of the auxiliary agent will advantageously be determined according to the genre of the tissue. In general, we will apply the principles developed for the finishing noble cellulose. A padding bath typical consists then as follows: 80 parts of auxiliary agent 920 parts water. After the application of the auxiliary, drying the substrate to a temperature at which the ancillary product can react. After drying, the substrate is ready for the transfer process which can be carried out as usual, continuously or discontinuously. It should be avoided that the auxiliary agent for use according to the invention reacts and reticle prematurely, it is to say before the diffusion of the colorant, so it would lose its solvency properties. Since a premature reaction can also occur during this transfer process itself, the catalyst should not be applied at the same time that. the auxiliary agent. It is advantageous to use the catalyst in the following manner: A second support 1° used auxiliary (also the auxiliary support itself for transfer printing) containing the catalyst, that provides, either against the side facing the surface of the substrate to be printed, either between the first auxiliary support and the heating device, or 2° employs a single auxiliary support containing the catalyst in addition to the dye. The protective paper often used in calendering can, in the described procedure under 1, act as the second auxiliary support. The secondary carriers according to 2 may contain the catalyst as component of the printing ink or they can receive the catalyst before or after printing, such as sputtering. Advantageously, the catalyst is applied on the back of the auxiliary support provided the valve is comprised of a permeable material, e.g. paper. The amount of catalyst required to attach generally varies between 0.5 and 3 g per square meter of substrate. The proportions of auxiliary agent depend on the substrate and vary for pure cotton between about 5 and 25% based on the weight of the substrate; for the blended fabrics, the proportion decreases at the composition, amounts rather high more beneficial. German Patent № 2,337 798 describes a transfer printing method of cellulose fibers with disperse dyes, in the presence of a bulk for cellulose. To secure the impressions so that they resist washing, must be operating in two stages: the prints obtained by the transfer method does not in effect are are wash and must be secured by applying cross-linking agents. The new method allows, in one operation, the absorption of the dye and its attachment by using auxiliary agents according to the invention. In the following examples, parts and percentages are by weight. Example 1 Flexographic printed paper with an ink composed of 10 parts of yellow dye no. 11,855 ci, 5 parts of ethyl cellulose, 70 parts of ethyl alcohol, 20 parts of ethyl acetate and 5 parts of ethyl glycol, then dry printing. Is then sprayed uniformly on the backside of the paper a solution of 100 g of MGCs. ^ ^ O O in 900 ml of water to apply 15 g of solution per square meter. The support is subsequently dried auxiliary. Impregnating a fabric of polyester/cotton mixed (mixing ratio 67/33) of a weight of 90 g/m ^ about, with a bath consisting of 75 parts of a melamine crroupes carrying a large number of mth thy a law and highly etherified inéthanol, and 925 parts water (liquor pick-80%), which is then dried to 9q °C. It provides the paper by the printed side on the prepared cloth - KOM the mth described above and this assembly is subjected, in a press 2 to paper, during 30 seconds to 20o °C to 4 kg/cm to a pressure, the paper is placed in front of the heated surface of the press. Excellent sensation intensely, lightfast, wherein the polyester fibers and cotton fibers emerge in the same tone, tone on tone. The printing is stable dry cleaning (trichloroethylene), as well as to wash at 60 °c performed with addition of commercially available detersive, the polyester/cotton mixed fabric one non-impregnated, subjected identically transfer recording, has printing irregular since the cotton fiber does not substantially absorb dye. The same results by using, in place of the melamine carrying many highly etherified methylol groups, the same amount of a tetramethyl ether of the tétraméthylolmélamine or the same amount of a mixture, in a weight ratio of 2/1, melamine-rich and highly etherified methylol groups and carbamate of n, O-dimethylol/3 a-butyldiéthylèneglycol. Example 2 A gravure paper is printed with an ink composed of 6 parts of the dye C.I. D®62015, 20 parts of a polymer of styrene and 79 parts of toluene, and dried printing (auxiliary support 1). Sprayed on one side of the polyester/cotton woven fabric (RAPs - 2 mixing pot 67/33) a weight of 180 g/m, a bath consisting of 100 parts of n, n-' a-dimethoxymethyl-4.5-dimethoxy-to-efchylene urea and 900 parts of water to apply bath by 150 g of square meter. The fabric is dried by hot air (100I C). 2, 2 Is sprayed, on plain paper with a weight of 20 g/m, 5 g/m of a 20% aqueous solution of ammonium chloride and dried (auxiliary support 2). The auxiliary support 1, the prepared cloth and the auxiliary carrier 2 are assembled in a sandwich configuration such that the tissue prepared is interposed between the auxiliary support 1 (printed side facing the fabric) and the auxiliary carrier 2; passed the "sandwiches" to 220®c by a calender transfer (45 seconds residence) by placing the auxiliary carrier 1 facing the heater. Excellent sensation strong solid washing and dry cleaning-resistant, wherein the polyester fibers and cotton fibers are dyed uniformly, tone on tone. Using a mixed fabric of polyester /' untreated cotton and proceeding for the rest as described above, excellent sensation irregular low intensity, since only the polyester portion of the mixed fabric has absorbed the dye. The same good results are obtained by applying to the support 2, instead of the ammonium chloride, the same amount of magnesium chloride or ammonium nitrate or zinc. Example 3 A stencil paper is printed, on rotary press, with an ink composed of 30 parts of the dye C.I. D®61505, 370 parts water, 400 parts of a thickener to 10% seed meal etherified and 200 parts of a thickener to 10% starch etherified and dried printing (auxiliary support 1). 2 A satin weave is impregnated cotton weight of 170 g/m with a bath consisting of 100 parts of a melanin carrying a high number of methylol groups and highly etherified methanol, 50 parts of methoxyethyl carbamate and 850 parts water (an AB - 100 sorption of bath 2 Spraying an aqueous solution with an 8 g/m 20% chloride 2 hydrated magnesium on plain paper with a weight of 25 g/m and dried (auxiliary support 2). The impregnated fabric and the supports are arranged one above the other in the following order: fabric, auxiliary support 2 (printed side facing the tissue), auxiliary support 2, and the assembled - gE is brought for 40 seconds in a press at 210 °c, under a near - 2 2 kg/cm. of sion, the auxiliary carrier 2 being placed facing the heater. Excellent sensation that resists uniform intensive dry cleaning and washing at 60 °c in the presence of detergents of commerce. By proceeding as described above, but using a non-impregnated cotton sateen, the surface of the satin weave is only slightly spotted after the transfer process: cotton does not substantially absorb dye. Example 4 2 A paper carry look-containing, by being made of, 2 g/m triethanolamine hydrochloride, is printed by offset printing with an ink composed of 10 parts of the dye of formula and 90 parts of a varnish having the following composition: 40 parts resin rosin modified phenol 20 parts of vegetable drying oils 10 parts of alkyd resin having a high proportion of oil 25 parts of mineral oil 5 parts of aerosol. On the other hand are impregnated with the polyester/cotton woven fabric (RAPs - 2 port 50/50 mixture), a weight of 120 g/m, with a bath consisting of 120 parts dimethoxymethyl urea and 880 parts water (liquor pick-90 It provides the paper printed with the printed side on the fabric and is treated, in a heated press, during 30 seconds to 220 °c 2 and a pressure of 3 kg/cm., the printed paper being disposed in front of the heater. Excellent sensation intense in which the cotton and polyester portion are dyed uniformly tone-which is solid and washing and dry cleaning. Similar results are obtained by replacing a part or the whole of the diméthoxyméthylurée, even with a liquor ratio, by a melamine carrying a large number of highly etherified methylol groups and methanol. Obtained similar quality prints by replacing the carbamate methoxyethyl in the example above by the same amount of carbamate of n, the n-dimethylol - / 5-methoxyethyl or the same amount of carbamate of n, an H-dimethoxymethyl - / O-methoxyethyl. Instead of the mixture of melamine carrying a high number of methylol groups, highly etherified, and methoxyethyl carbamate, you can use the same amount of a condensate mixed highly etherified methanol, obtained from 1 mole of AlB24C4 1amine, 1 mole of carbamate methoxyethyl and 6 moles of formaldehyde. We obtain the same good results. Example 5 Paper is sprayed on a 10% aqueous solution of zinc nitrate to obtain about 2 g of zinc nitrate per square meter and dried. Then printing the paper as described in example 2, but using the dye C.I. № 61105. Printed stencil on the other hand, a rotary press, a cotton poplin a weight of 120 g/m, entirely on one side, with a paste composed of 100 parts of tétraméthoxyméthylmélamine, 50 parts of n, n-' bis-ethoxymethyl-urone, 5 parts of the salt ammonic a lightly crosslinked polymer of acrylic acid, obtained state precipitate (thickener) and 845 parts water and dried at 100 °c. The amount applied is from about 15 g/m, expressed as dry extract. It provides the paper printed with the printed side on the side to be printed from the poplin impregnated and treated to 220 °c transfer in a calender, with a residence of 45 seconds, the paper being positioned in front of the heating device of the calender. Excellent sensation intensive uniform, solid to washing and dry cleaning. A non-impregnated cotton poplin is hardly tinted under conditions otherwise similar. Example 6 A stencil paper is printed, on rotary press, with an ink composed of 30 parts of the dye of formula 30 parts of hydrated magnesium chloride, 340 parts water and 400 parts of a thickener to 10% starch etherified and dried printing. On the other hand size is a mixed fabric of polyester/cotton as described in the example 1, with a compound of the bath 50 parts of tetramethyl ether of 1 'hexamethylolmelamine, 30 parts of n, n-' di-methoxymethyl-4-methoxy-5.5-dimethylpropylene urea and 920 parts water (liquor pick-80 It provides the paper printed with the printed side on the impregnated fabric and is treated, in a heated press, during 30 seconds to 220 °c under a pressure of 5 kg/cm., the paper is placed in front of the heated portion of the press. Excellent sensation intensive uniform, tone-in, very good lightfastness, washing and dry cleaning. Using a non-impregnated paper through and for the remainder similarly, only the dyeing that on the polyester portion of the mixed fabric and printing is uneven and much less intense. The same good results are obtained by replacing the 30 parts of the derived from propylene urea above by 15 parts that a carbamate of formula HO (^ 0 02)grams THE C ^ ^ ^ C IS THE O-COR. Example 7 A stencil paper is printed, on rotary press, with an ink composed of 30 parts of the dye of formula 370 parts water, 400 parts of a thickener to 10% seed meal etherified and 200 parts of a thickener to 10% starch etherified and dried printing. Then printing the back side of the same paper with a printing paste composed of 50 parities maleic acid, 350 parts of water, 400 parts of a thickener to 10 On the other hand are impregnated with a velour cotton of a weight of 250 2 g/m with a bath consisting of 100 parts of a melamine carrying a high number of methylol groups, etherified methanol, 50 parts of methoxyethyl carbamate and 850 parts water (liquor pick-100 It provides the auxiliary support by the side color-printed web on the side of the pile and is treated at a temperature of 220 °c in a calender transfer (40 seconds residence). Excellent sensation strong, solid to washing and dry cleaning. Using an untreated cotton velvet and proceeding for the remainder similarly, there is only a very light dyeing the surface of the pile after the transfer process. Laying on the backside of the velour cotton impregnated, before the transfer process, a second auxiliary support prepared as described in example 3 to (auxiliary support 1 of the example 3), by the printed side, and proceeding for the remainder similarly, obtained in a single operation printing different intense on both the front and back of the velvet, which are solid to washing and dry cleaning. Example 8 Gravure printed paper containing, by its pre - 2 liftable, about 2 g/m tartaric acid, with an ink composed of 6 parts of the dye C.I. № 11005, 20 parts of a polymer of styrene and 79 parts of toluene and dried printing (auxiliary support). On the other hand are impregnated with a knitted fabric having a weight of cotton 140 g/m with a bath consisting of 75 parts of a melamine containing a large number of methylol groups, etherified methanol, of 75 parts of n, n-' a-dimethoxymethyl-4.5-dimethoxy-ethylene urea and 850 parts water. The liquor pick-amounts to 100%. The knitted fabric is dried impregnated at 110 °c. It provides the auxiliary support by the printed side on the knit fabric and treated it during 40 seconds to 220 °c transfer in a calender. Excellent sensation strong, solid to washing and dry cleaning. Using an untreated cotton knit and proceeding for the remainder similarly, there is only a very light dyeing the surface of the knitted fabric. A process for the transfer printing of fabrics containing or consisting of cellulose fibers, by using transfers, wherein the fabric is impregnated with aqueous solutions of compounds which are both solvents for the transfer dyes and potential crosslinking agents for cellulose, dried and printed by the transfer process, in the presence of a cross-linking catalyst, applied from a transfer, with sublimable dyes or optical brighteners. 1, - Transfer printing method of cellulose fibers and of blended fabrics containing such fibers, using auxiliary supports, the method characterized by the fact that iœprègne&etissu moistened with water by compounds by tightening of both solvents for dyes transfer and crosslinkers potentials for cellulose, drying the fabric and prints it, by the transfer printing process with dyes subliœahles or optical brighteners, in the presence of a catalyseyr cross-links the applied on an auxiliary support, 2, - The auxiliary agents of this invention are derivatives of urea or melamine-di - or polyfunctional éthêrifiés carrying methylol groups, as well as carbadates, in particular, is used, as an auxiliary agent, a mixture of melamine high methylol groups, etherified methanol, and methoxyethyl carbamate. 3) The catalysts are metal salts or salts of volatile acids and/ammonic or volatile acids, in particular of the'd ' a-ANNs monium chloride or magnesium chloride, 4, - Auxiliary support for implementing the method according to paragraph 1, containing the catalyst and, optionally, the printing inks, the catalyst preferably being on the reverse (with respect to the imprint), 5" - the colorant is of the formula ii and is optionally in combination with other dyes and/or brighteners throughput opti er,