Thermotransfer process for printing synthetic fibre materials with multi-color effects, and carrier for performing the process

The present invention relates to a thermal dry transfer printing process for printing synthetic fibre materials with multi-colour effects, in which process an intermediate carrier is printed, in any chosen sequence,
(1) in places with at least one reserve printing paste or reserve printing ink, and
(2) with a printing paste or printing ink for printing the base, the reserve printing paste or ink (1) containing at least:
(a) one reserving agent,
(b) one thickener,
(c) optionally one non-reservable, sublimable disperse dye,
(d) optionally one curing catalyst and
(e) one organic solvent and/or water; and the printing paste or ink (2) for printing the base containing at least:
(b) one thickener,
(g) one reservable, sublimable disperse dye,
(e) one organic solvent and/or water and
(f) optionally one binder;
the intermediate carrier is dried; brought into contact with the fibre material to be printed, and both are subjected to a heat treatment at elevated temperature, optionally with the application of pressure, until the unreserved dyes are transferred from the intermediate carrier to the fibre material, and the intermediate carrier is then separated from the printed fibre material. The intermediate carrier for performing the process, which carrier is printed in places with at least one reserve printing paste or ink (1) and with a printing paste or ink for dyeing the base (2), of the given compositions, and the fibre materials printed by the process form further subject matter of the present invention.
The reserve printing pastes or inks (1) [known also as resist printing pastes or inks] contain as a rule: 10 to 25% of a reserving agent (b) [known also as resisting agent], 0.2 to 15%, preferably 0.5 to 10%, of a thickener (b), 0 to 10% of a non-reservable dye (c), 0 to 2.5, preferably 0 to 1% of a curing catalyst (d), and 50 to 90% of water and/or of an organic solvent (e); and the printing pastes or inks (2) for printing the base: 0.2 to 15%, preferably 0.5 to 10%, of a thickener (b), 40 to 98% of water and/or of an organic solvent (e), 0 to 5% of a binder (f), and 1 to 20%, preferably 2 to 10%, of a reservable dye (g).
The percentages given for the constituents (a), (b), (c), (g), (d) and (f) relate to pure (i.e. 100%) reserving agents, thickeners, dyes, curing catalysts and binders; and all percentage values are percent by weight, the sum of the weight percentages for the various printing pastes or printing inks always adding up to hundred percent by weight.
In general, both the reserve printing pastes or inks (1) and the printing pastes or inks (2) for printing the base are applied to the intermediate carriers, depending on the type and nature of the intermediate carriers, in such a way that the amount deposited on the surface of the intermediate carrier is about 8 to 25 g/m.sup.2.
The reserving agents (a) used are preferably highly etherified aminoplast pre-condensates, that is to say, highly etherified addition products of formaldehyde or of formaldehyde-forming agents, for example paraformaldehyde, hexamethylenetetramine or trioxane, with N-methylolatable nitrogen compounds. These aminoplast pre-condensates are present on the intermediate carrier in at least a partially cured or crosslinked condition, that is to say, as aminoplast resins.
Methylolatable nitrogen compounds which may be mentioned are 1,3,5-aminotriazines such as N-substituted melamines, for example butylmelamine, N-trihalomethylmalamines, triazones, as well as guanamines, for example benzoguanamines, acetoguanamines and diguanamines. Also suitable are: cyanamide, acrylamide, alkyl- or arylureas and -thioureas, alkyleneureas or -diureas, for example urea, thiourea, urons, ethyleneurea, propyleneurea, acetylenediurea or 4,5-dihydroxyimidazolidone-2 and derivatives thereof, for example 4,5-dihydroxyimidazolidone-2 substituted in the 4-position on the hydroxyl group with the radical --CH.sub.2 --CH.sub.2 --CO--NH--CH.sub.2 OH, and carbamates of lower alkanols, such as carbamic acid-methyl, -ethyl or -hydroxyethyl esters. Preferred among these nitrogen compounds which can be methylolated are urea and, in particular, melamine.
Accordingly, preferred etherified aminoplasts are in particular etherified aminoplast formers, for example etherified dimethylolurea, dimethylolethyleneurea, dimethylolpropyleneurea, etherified, optionally partially methoxylated dimethyloldihydroxy-ethyleneurea, etherified dimethyloluron, trimethylolmelamine, trimethoxymethylmelamine, pentamethylolmelamine, hexamethylolmelamine, hexamethoxymethylmelamine, dimethylolmethyltriazine, dimethylolhydroxyethyltriazone, dimethylolhydroxyethyltriazone, dimethylolmethylcarbamate and 4-methoxy-5-dimethyldimethylolpropyleneurea, with etherified dimethylolurea, dimethyleneethyleneurea, particularly etherified pentamethylolmelamine and hexamethylolmelamine being especially preferred.
Both predominantly etherified monomolecular and etherified higher precondensed aminoplasts are suitable as aminopolast pre-condensates.
The reserving agents (a) employed are preferably water-soluble ethers of the aforementioned aminoplast pre-condensates with alkanols having 1 to 4 carbon atoms, such as ethanol, n-propanol, isopropanol, n-butanol or in particular methanol. Of major interest as reserving agents (a) are hence pentamethylolmelaminetetramethyl ether and especially hexamethylolmelaminehexamethyl ether; as a commercial product, hexamethylolmelaminehexamethyl ether is not completely etherified but is a hexamethylolmelamine highly etherified up to 90 to 98% with methanol.
Suitable as component (b) are essentially all thickeners customarily used in textile printing, of both natural and synthetic origin. Examples of such thickeners which may be mentioned are: alginates, optionally etherified best grade flour, etherified cellulose or starch and homo- or copolymers based on acrylic acid or maleic anhydride. Preferred natural thickeners (b) for aqueous printing pastes (1) or (2) are in particular sodium alginate, an etherified potato starch or an etherified guar or locust bean flour; and preferred thickeners (b) for solvent-containing printing inks (1) or (2) are especially cellulose ethers or cellulose esters, for example hydroxyethylcellulose, cellulose acetobutyrate, preferably hydroxypropylcellulose, cellulose acetopropionate and, in particular, ethylcellulose and carboxymethylcellulose.
Preferred synthetic thickeners (b) for aqueous printing pastes (1) or (2) are especially copolymers based on ethylene/maleic anhydride; and preferred synthetic thickeners (b) for solvent-containing printing inks (1) or (2) are particularly homopolymers of acrylic acid or of acrylic acid amide, copolymers of acrylic acid or of acrylic acid amide, or copolymers of acrylic acid and of acrylates.
The thickeners used as component (b) are as a rule prepared as aqueous solutions having a 1 to 15, preferably 2 to 8, percent by weight content of ingredients. They can also be constituents of formulations of the dyes (c) and (g).
The dyes used as components (c) and (g) in printing pastes or inks (1) and (2) are the customary sublimable disperse dyes suitable for the thermotransfer printing process, which convert at 160.degree. to 220.degree. C. into the vapour state, that is to say, dyes of which the vapour pressure at, for example, 200.degree. C. is higher than 10.sup.-5 bar.
The sublimable disperse dye used as component (g) in the printing paste or ink (2) for printing the base of the intermediate carrier is reservable (resistible), that is, it reacts at the temperatures used in the transfer printing process with the component (a) in the reserve printing paste or ink (1). The result of this is that this reservable dye, in the thermotransfer printing process, is not transferred to the fibre material at the places where the intermediate carrier is provided with a reserving agent. The obtainment of patterned reprints is rendered possible by virtue of this reserving of the dye.
The sublimable disperse dye optionally used as component (c) in the reserve printing paste or ink (1) is not reservable, that is to say, it is inert to the reserving agent used as component (a), so that the dye can be transferred unhindered from the intermediate carrier to the fibre material. If the reserve printing paste or ink (1) contains no component (c), there are obtained so-called white resists, for example white to faintly coloured patterns on a dyed background. With the presence of non-reservable dyes (c) in the reserve printing paste or ink (1), there are on the other hand obtained so-called colour resists. When for example a yellow dye is used as component (c) in the reserve printing paste or ink (1) and a reservable blue dye as component (g) is used in the printing paste or ink (2) for printing the base (ground), yellow patterns on a blue background are obtained. With use of a single reserve printing paste or ink (1), two-colour effects are obtained, and with use of several reserve printing pastes or inks (1), multi-colour effects are obtained.
By the terms reservable and non-reservable dyes (c) and (g) are meant within the scope of this invention only those dyes which, with the given amount of reserving agent (a) and optionally of dye (c) in the reserve printing paste or ink (1), and also of dye (g) in the printing paste or ink (2), with the given deposited amount of the printing pastes or inks (1) and (2), with chemical reaction of the dyes (g) with the reserving agent (a), and optionally with the absence of a chemical reaction of the dyes (c) with the reserving agent (a), exhibit the behaviour described in the foregoing. The process according to the invention thus differs from known processes in which, for example, a resin or a so-called blocking agent is applied in any desired depth of deposit, that is to say, in any desired thickness of coating, in given areas over the paste or ink for printing the base, so that at the places at which the blocking agent has been applied, the dye is prevented, particularly on account of physical processes, from being transferred from the intermediate carrier to the fibre material to be printed. In the case of known processes of this type, the patterns obtained are frequently not entirely uniform, and they often have contours which are poorly defined or aureoles.
The dyes (c) and (g) used in the printing pastes (1) and (2) belong, inter alia, to the groups comprising nitro dyes of the aniline series, azo dyes of the benzene series, as well as anthraquinone, quinoline, pyrazolone, triazole, pyridone or styryl dyes, and are described, for example, in Colour Index, 3rd Edition, 1971, under the heading "Disperse dyes", in the Belgian Pat. No. 584,558; in the British Pat. Nos. 959,314, 1,189,026, 1,127,721, 1,211,149, 1,254,021, 1,344,353, 1,359,206, 1,334,114, 1,445,201 and 1,460,742; in the German Offenlegungsschriften Nos. 2,739,174 and 2,739,314; and in the journal "Man-made Textiles in India", pages 40-43, January 1977.
The non-reservable, sublimable disperse dyes used as component (c) in the reserve printing paste or ink (1) contain as a rule no amino or hydroxyl groups capable of reacting with the component (a) at 160.degree. to 220.degree. C., optionally however a hydroxyl group, secondary amino group or primary amino group, each of which is bound on an aromatic nucleus and is inert to the component (a), the hydroxyl group having to be capable of forming with adjacent carbonyl, azo or nitro groups a hydrogen bridge, and the primary amino group having to be sterically hindered by a substituent in the o-position.
Disperse dyes of the following formulae may be mentioned as examples of non-reservable disperse dyes of the aforementioned type: ##STR1##
The reservable, sublimable disperse dyes used as component (g) in the printing paste or ink (2) contain as a rule at least one amino or hydroxyl group capable of reacting with the component (a) at 160.degree. to 220.degree. C. The reactive amino or hydroxyl group is preferably a hydroxyl or amino group bound on an aliphatic chain, a hydroxyl or primary amino group bound on an aromatic nucleus, or a secondary amino group present as member of a pyrazolone, triazole or pyridone ring, the hydroxyl group being free from adjacent carbonyl, azo or nitro groups, and the primary amino group from substituents in the o-position.
It can be determined by simple tests with preferably dye-free reserve printing pastes or inks (1) whether or not a given sublimable disperse dye of the printing paste or ink (2) is reservable, that is to say, capable of reacting with the reserve printing paste or ink (1), and hence no longer transferable from the intermediate carrier to the fibre material.
Disperse dyes of the following formulae may be mentioned as examples of reservable dyes of the above type: ##STR2##
The dyes used as components (c) and (g) are as a rule commercial 30 to 60 percent by weight formulations. When aqueous printing pastes (1) and (2) are used for the reserve and for printing the base (or ground), the formulations contain, in addition to water, generally dispersing agents, for example lignin sulfonates, fatty alcohol polyglycol ethers, aromatic sulfonic acids, for instance naphthalenesulfonic acids or condensation products thereof with formaldehyde, one of the aforementioned thickening agents, as well as preferably further auxiliaries, such as wetting agents, for example fatty acid alkanolamides, ethyleneoxy adducts from fatty alcohols or fatty amines, antifreeze agents and agents maintaining the product moist, for example ethylene glycol, propylene glycol, glycerol or sorbitol, preserving agents, for example hexamethylenetetramine-chlorallyl derivatives, defoaming agents, for example silicone oil emulsions and, if the employed dyes are in pulverulent form, anti-dust agents, for example a sulfonated mineral oil.
When printing inks (1) and (2) containing solvents are used for the reserve and for printing the base, the formulations contain as solvents for example an aliphatic alcohol or ketone, or an aromatic hydrocarbon having in each case at most 8 carbon atoms, preferably an alkanol having 1 to 4 carbon atoms. The following may be mentioned as examples of solvents of this type: chlorobenzene, toluene, xylene, benzene and methyl ethyl ketone, preferably however propanol, methanol and in particular ethanol and isopropanol. These printing inks as a rule contain, besides the solvent, preferably only one of the above-mentioned thickeners as auxiliary, especially a cellulose ether or ester, for example hydroxyethylcellulose or cellulose acetopropionate or in particular ethylcellulose.
The curing catalysts used as component (d) are, inter alia: acid or potentially acid catalysts, for example citric acid, tartaric acid, phosphoric acid, ammonium chloride, zinc chloride, zinc nitrate, preferably magnesium chloride or in particular 2-amino-2-methyl-1-propanol hydrochloride. Also sulfates and phosphates of aminomethylpropanol are suitable.
The optional component (d) acts as a curing catalyst for the component (a) used as reserving agent. The concomitant use of an acid catalyst as component (d) is necessary only where natural thickeners are employed as component (b), which in general are neutral to alkaline. If alternatively synthetic thickeners are used, which produce an acid reaction under the transfer conditions, that is, at elevated temperatures, it is not necessary to concomitantly use an acid catalyst for curing the reserving agent. The curing catalyst used as component (d) is usually in the form of a 20 to 30 percent by weight aqueous solution.
In the case of the solvents used as component (e) in the printing inks (1) or (2) for the reserve printing or for printing the base, these are preferably the same solvents as those already mentioned with regard to the solvent-containing dye formulations.
The binders optionally used as component (f) only in the printing pastes or inks (2) for printing the base are preferably homopolymers of the vinyl series, for example polyvinyl alcohol or polyvinyl acetate. Polymers of this type are usually in the form of 10 to 30 percent by weight aqueous solutions.
Preferred reserve printing inks (1) contain: 10 to 25% of a highly etherified aminoplast pre-condensate as reserving agent (a), 0.5 to 15%, preferably 4 to 10% and particularly 0.5 to 15%, of a cellulose ester or ether as natural thickener (b), 0 to 10% or 2 to 10%, as component (c), of a non-reservable disperse dye which, as already mentioned, is inert to the component (a), 0.3 to 2.5%, especially 0.3 to 1%, of magnesium chloride or 2-amino-2-methyl-1-propanol hydrochloride as curing catalyst (d), 50 to 90% of an aliphatic alcohol or ketone or of an aromatic hydrocarbon having in each case at most 8 carbon atoms, as solvent (e), and 0 to 20%, or 5 to 20% of water.
Preferred reserve printing pastes (1) contain either 10 to 25% of a highly etherified aminoplast pre-condensate as reserving agent (a), 2 to 10% of a sodium alginate, of an etherified starch or of an etherified high grade flour, as natural thickener (b), 0 to 10%, or 2 to 10%, as component (c), of a non-reservable disperse dye which, as already mentioned, is inert to the component (a), 0.3 to 2.5%, particularly 0.5 to 1.5%, of magnesium chloride or 2-amino-2-methyl-1-propanol hydrochloride as curing catalyst (d), and 50 to 90% of water; or 10 to 25% of a highly etherified aminoplast pre-condensate as reserving agent (a), 0.2 to 2%, particularly 0.5 to 2%, of a mono- or copolymer of acrylic acid or of acrylates or of a copolymer based on ethylene/maleic anhydride, as synthetic thickener (b), 0 to 10%, or 2 to 10%, as component (c), of a disperse dye which, as already mentioned, is inert to component (a), and 40 to 90% of water.
Preferred printing inks (2) for printing the base contain: 0.5 to 15%, preferably 4 to 10%, and especially 0.5 to 1.5%, of a cellulose ester or ether, as thickener (b), 40 to 95% of an aliphatic alcohol or ketone or of an aromatic hydrocarbon having in each case at most 8 carbon atoms, as solvent (e), 2 to 20%, particularly 2 to 10%, of a reservable dye (g) of the given type, 0 to 5%, or 3 to 5%, of a polyvinyl alcohol or polyvinyl acetate, as binder (f), and 0 to 20% of water; and preferred printing pastes (2) for printing the base contain: 0.2 to 10%, particularly 5 to 10%, of an alginate, of an optionally etherified high grade flour, of an etherified cellulose or starch, or of a homo- or copolymer based on acrylic acid, acrylic acid amide or maleic anhydride, as thickener (b), 2 to 20%, especially 2 to 10%, of a reservable dye (g) of the given type, 0 to 5%, or 3 to 5%, of a polyvinyl alcohol or polyvinyl acetate, as binder (f), and 25 to 98% of water.
The printing pastes are in general preferred to the printing inks.
Suitable fibre materials which can be printed according to the invention are in particular fibre materials in the form of broad widths of fabric, for example carpets, fleeces, preferably knitted goods and especially fabrics. The synthetic fibres concerned are particularly cellulose acetate fibres, for example cellulose 21/2-acetate and preferably cellulose triacetate, and fully synthetic fibres made from, inter alia, acrylonitrile homopolymers or acrylonitrile copolymers, also called modacrylic fibres, in which advantageously the acrylonitrile proportion is at least 50 percent by weight of the copolymer, and in which usually other vinyl compounds are used as comonomers; preferably polyamide fibres, for example those formed from poly-2-caprolactam, polyhexamethylenediamine-adipate or poly-.omega.-aminoundecanoic acid; or modified polyamide fibres, for example those from polycarboxylic acid amides from bis-(p-aminocyclohexyl)-methane and decanedicarboxylic acid; and especially polyester fibres, for example those which are derived from terephthalic acid, such as for instance poly(ethylene glycol terephthalate) or poly(1,4-cyclohexyldimethylene terephthalate). Polyester materials are particularly well suited to be printed by the process according to the invention. Also mixtures of the fibre materials mentioned are suitable.
Suitable for printing cellulose acetate fibres and modified polyamide fibers of the type mentioned in the foregoing are in particular the non-reservable dyes of the formulae (1) to (5) and the reservable dyes of the formulae (8) to (15) and (21); suitable for printing polyacrylonitrile fibres are particularly the non-reservable dyes of the formulae (1), (4), (6) and (7) and the reservable dyes of the formulae (8), (9), (11) to (15) and (21); suitable for printing polyamide fibres are especially the non-reservable dyes of the formulae (1) to (7) and the reservable dyes of the formulae (9), (14), (15), (21) and (25); and suitable for printing polyester fibres are especially the non-reservable dyes of the formulae (1) to (5) and the reservable dyes of the formulae (8) to (15) and (21). Thus the non-reservable dyes (1) to (7) and the reservable dyes of the formulae (8) to (15), (21) and (25) are preferred to the reservable dyes (16) to (20) and (22) to (24).
It is possible with an advantageous combination of these preferred dyes to obtain virtually all conceivable colours or shades of the visible spectrum.
The widest variety of printing techniques are used for printing the intermediate carrier, such as the flat printing process (for example offset), the electrostatic printing process, screen printing (for example flat screen printing, rotary flat printing and silk screen printing), the high pressure process (for example book printing, flexographic and relief printing) and especially the gravure printing process (for example roller printing) and the rotary printing process (for example discharge printing and deep engraving printing).
The viscosity of the printing inks and pastes (1) and (2) has to be adjusted to suit the particular printing technique used, an adjustment which is effected by varying the amount of thickener (b) in the printing inks or pastes. This applies also to the amount of printing ink or pastes (1) and (2) applied to the intermediate carrier. The deposit per unit area in the screen printing process (rotary flat printing) is for example preferably 15 to 20 g/m.sup.2, and in the gravure printing process it is for example 8 to 12 g/m.sup.2.
The reserving effect of component (a) in the reserve printing paste or ink is independent of the sequence in which the printing inks or pastes (1) and (2) are applied to the intermediate carrier. If however the reserve printing pastes or inks (1) are applied first and then the printing pastes or inks (2) for printing the base, there is no need for the otherwise expedient markings of the areas printed with the paste or ink (1) with suitable agents, for example with non-transferable dyes or fluorescent substances, which would render the process according to the invention difficult.
Whereas the printing with the reserve printing paste or ink (1) is always performed in places or on specific areas, the paste or ink (2) for printing the base or background is preferably printed over the whole surface. A so-called intermediate drying is optionally performed between printing with the reserve printing paste or ink (1) and printing with the paste or ink (2) for printing the base. Preferably, however, the intermediate carrier is printed without intermediate drying in one single operation. The intermediate carrier is dried after printing with the two pastes or inks (1) and (2). This drying and any intermediate drying are preferably performed at 80.degree. to 140.degree. C.
The intermediate carriers printed according to the invention have the advantage that they can be produced in a single economical operation. They are fast to rubbing and are able to be stored, and can be used at any time for printing the fibre materials. For printing the fibre materials, the intermediate carrier is brought into contact with the fibre material, and both are then subjected, for example in an ironing press or calender with application of pressure, to a heat treatment, preferably at 190.degree. to 220.degree. C., for 20 to 90 seconds. It is also possible however to apply a vacuum, in the manner described for example in the British Patent Specification No. 1,312,529.
The essential advantage of the process according to the invention is that multi-colour effects are obtained on the fibre materials in one single and economical operation, the patterns produced being as numerous and fine as desired and having the widest variety of shades and extemely sharp outlines without the slightest sign of aureoles.

Parts and percentages given in the following Examples are in all cases in weight units.
EXAMPLE 1
An intermediate carrier made of paper is printed by the rotary printing process using the following printing pastes with a surface application in each case of 15-20 g/m.sup.2 :
(A) reserve printing paste consisting of 450 to 500 parts of a copolymer based on ethylene/maleic anhydride (2%) as thickener; 100 to 200 parts of hexamethylolmelaminehexamethyl ether as reserving agent; and 50 parts of the yellow dye of the formula (1) (48%): paste made up with water to 1000 parts;
(B) reserve printing paste containing the same amounts of the thickener and reserving agent of reserve printing paste (A), but with 100 parts of the red dye of the formula (2) (54%);
(C) reserve printing paste containing the same amounts of the thickener and reserving agent employed in reserve printing paste (A), but containing a mixture of 50 parts of the yellow dye of the formula (1) (48%) and 10 parts of the blue dye of the formula (4) (48%);
(D) reserve printing paste containing the same amounts of the thickener and reserving agent employed in reserve paste (A), but containing no dye;
(E) printing paste for printing the base, consisting of 450 to 500 parts of a mixture of 50% of an etherified potato starch and 50% of an etherified locust bean flour (8%) as thickener, 150 parts of a mixture of 87% of polyvinyl alcohol and 13% of polyvinyl acetate (20%) as binder, and a mixture of 20 parts of the orange-coloured dye of the formula (9) (43%) and 80 parts of the blue dye of the formula (14) (44%): paste made up with water to 1000 parts.
The pastes (A), (B), (C) and (D) are applied in places, and the paste (E) over the whole surface, the pastes (A) to (D) being applied first and the paste (E) last.
The printed intermediate carrier is dried at 100.degree. C. for 5-10 seconds. It is stable in storage, fast to rubbing and usable at any point of time for printing synthetic fibre materials by the thermal dry transfer printing process.
For printing the fibre material, the intermediate carrier and a polyester fabric having a weight per unit area of 100 g/m.sup.2 are pressed together in an ironing press for 30 seconds at 210.degree. C. under an excess pressure of 0.04 to 0.06 bar. After transfer of the non-reserved dye from the intermediate carrier to the polyester fabric, there are obtained on the fabric yellow, mauve, green and light-blue patterns having sharp contours, without aureoles, on a violet background (base).
Identical results are obtained by using firstly the paste (E) and secondly the pastes (A) to (D); or when the pastes are used, in any sequence, in the gravure printing process with only 150 to 250 parts of the respective thickeners given for printing pastes (A) to (E).
EXAMPLE 2
The procedure is carried out in the manner described in Example 1 but using as thickener in the printing pastes (A), (B), (C) and (D) 600 parts of a mixture of 50% of an etherified potato starch and 50% of an etherified locust bean flour (8%) together with 15 parts of 2-amino-2-methyl-1-propanol hydrochloride (36%) as acid curing catalyst; and as dye in the printing paste (E) a mixture of 80 parts of the yellow dye of the formula (8) (50%), 40 parts of the orange-coloured dye of the formula (9) (43%) and 140 parts of the blue dye of the formula (14) (44%).
The intermediate carrier obtained is, as in Example 1, likewise storage stable and fast to rubbing. On application of this carrier, there are obtained on polyester fabric yellow, mauve, green and light-blue patterns having sharp contours, without aureoles, on a black background.
EXAMPLE 3
The procedure is carried out in the manner described in Example 1 but using as thickener in the printing pastes (A), (B), (C) and (D) 450 parts of sodium alginate (10%), together with 15 parts of 2-amino-2-methyl-1-propanol hydrochloride (36%) as acid curing catalyst, and as dye in the printing paste (E) a mixture of 70 parts of the yellow dye of the formula (8) (50%) and 30 parts of the blue dye of the formula (14) (44%).
The intermediate carrier obtained is, as in Example 1, likewise storage stable and fast to rubbing. On application of the carrier, there are obtained on the polyester fabric golden yellow, light-yellow, red and light-green patterns having sharp contours, without aureoles, on a dark-green background.
EXAMPLES 4 TO 33
The procedure is carried out in the manner described in Example 1 but using in places a single reserve printing paste containing one of the thickeners given in the Examples 1 to 3, optionally together with aminomethylpropanol hydrochloride as catalyst, in all cases hexamethylolmelamine-hexamethyl as reserving agent, and a dye or a dye mixture according to the following Table I; and then using over the whole surface a printing paste for printing the base, which paste contains the thickener and binder given in Example 1 for the printing paste (E), and a dye or a dye mixture according to the following Table I.
There are likewise obtained intermediate carriers which are storage stable and fast to rubbing, as given in Example 1; and on application of these carriers, there are obtained on polyester fabric the patterns listed in the following Table I, which have sharp contours without aureoles.
TABLE I__________________________________________________________________________ Dye in the printing paste forDye in reserve printing paste (appli- printing the base (applicationcation in places) to whole surface) Patterns obtainedExample amount content amount content colour of colour ofNo. parts formula % colour parts formula % colour the pattern the__________________________________________________________________________ base4 100 (2) 54 red 60 (9) 43 orange dark red orange5 50 (1) 48 yellow 50 (9) 43 orange dark green light red G* G* 50 (4) 48 blue 50 (11) 33 pink6 50 (1) 48 yellow 40 (9) 43 orange orange dark red G* G* 40 (2) 54 red 40 (12) 41 red7 50 (1) 48 yellow 40 (9) 43 orange light green claret G* G* 10 (4) 48 blue 40 (10) 45 ruby8 50 (3) 40 blue 60 (10) 45 ruby blue ruby9 50 (1) 48 yellow 80 (11) 33 pink green pink G* 15 (4) 48 blue10 50 (3) 40 blue 50 (11) 33 pink blue dark red G* 50 (12) 41 red11 40 (1) 48 yellow 80 (12) 45 red yellow dark red12 100 (2) 54 red 60 (13) 42 violet red violet13 50 (1) 48 yellow 50 (12) 41 red dark violet G* G* 50 (4) 48 blue 50 (14) 44 blue green14 50 (1) 48 yellow 80 (14) 44 blue golden blue G* 10 (2) 54 red yellow15 90 (2) 54 red 20 (8) 42 yellow dark dark G* G* 10 (3) 40 blue 80 (14) 44 blue red blue16 50 (1) 48 yellow 200 (15) 43 blue light light G* 10 (4) 48 blue green blue17 50 (1) 48 yellow 20 (8) 42 yellow yellow blue G* 180 (15) 43 blue18 50 (1) 48 Yellow 50 (8) 42 yellow light blue- G* G* 10 (4) 48 blue 50 (10) 45 blue green green19 100 (2) 54 red 40 (8) 42 yellow red dark G* 160 (15) 43 blue green20 60 (4) 48 blue 80 (8) 42 yellow blue light G* 10 (15) 43 blue green21 90 (2) 54 red 80 (18) 42 yellow dark olive G* G* 10 (3) 40 blue 20 (14) 44 blue red green22 50 (1) 48 yellow 60 (9) 43 orange orange light G* G* 10 (2) 54 red 10 (14) 44 blue brown23 50 (1) 48 yellow 60 (9) 43 orange dark maroon G* G* 50 (4) 48 blue 80 (15) 43 blue green24 50 (1) 48 yellow 20 (8) 42 yellow light dark G* 10 (4) 48 blue 40 (9) 43 orange G* green brown 40 (14) 44 blue25 50 (1) 48 yellow 10 (8) 42 yellow orange dark G* G* 10 (2) 54 red 40 (9) 43 orange brown 40 (14) 44 blue26 100 (2) 54 red 5 (9) 43 orange red violet 5 (10) 45 ruby G* 80 (14) 44 blue27 50 (1) 48 yellow 10 (9) 43 orange light green navy blue G* 80 (14) 44 blue28 50 (1) 48 yellow 20 (9) 43 orange dark navy blue G* G* 10 (4) 48 blue 80 (14) 44 blue green29 100 (2) 54 red 80 (8) 42 yellow red black 40 (9) 43 orange G* 140 (14) 44 blue30 50 (1) 48 yellow 80 (8) 42 yellow light green black 40 (9) 43 orange G* 140 (14) 44 blue31 60 (4) 48 blue 80 (8) 42 yellow blue black 40 (9) 43 orange G* 140 (14) 44 blue32 50 (1) 48 yellow 80 (8) 43 yellow orange black G* G* 10 (2) 54 red 40 (9) 43 orange 140 (14) 44 blue33 90 (2) 54 red 80 (8) 42 yellow claret black G* G* 10 (3) 40 blue 40 (9) 43 orange 140 (14) 44 blue__________________________________________________________________________ G* = mixture
EXAMPLES 34 TO 70
The procedure is carried out in the manner described in Example 1 but using in places a single reserve printing paste containing one of the thickeners given in the Examples 1 to 3, optionally together with 2-amino-2-methyl-1-propanol hydrochloride as catalyst, and in all cases hexamethylolmelamine-hexamethyl ether as reserving agent, but no dye; and then applying over the whole surface a printing paste for printing the base, the paste containing the thickener and binder given in Example 1 for the printing paste (E), and a dye or dye mixture according to the following Table II. There are obtained intermediate carriers which are storage-stable and fast to rubbing, as in Example 1; and on applying these carriers to polyester fabrics, there are obtained on the base light-coloured patterns having sharp contours and displaying the shades of colour given in the following Table II.
TABLE II______________________________________Ex-am- Dyeple amount content ResultingNo. parts formula % colour colour of base______________________________________34 80 (8) 42 yellow yellow35 60 (9) 43 orange orange36 50 (9) 43 orange light red G* 50 (11) 33 pink37 40 (9) 43 orange claret G* 40 (12) 41 red38 40 (9) 43 orange dark red G* 40 (10) 45 ruby39 60 (10) 45 ruby ruby40 80 (11) 43 pink pink41 50 (11) 43 pink light G* 50 (12) 41 red claret42 80 (12) 41 red dark claret43 60 (13) 42 violet light violet44 50 (12) 41 red dark G* 50 (14) 44 blue violet45 80 (14) 44 blue blue46 20 (8) 42 yellow dark G* 80 (14) 44 blue blue47 200 (15) 43 blue sky-blue48 20 (8) 42 yellow blue-green G* 180 (15) 43 blue49 50 (8) 42 yellow dark green G* 50 (14) 44 blue50 40 (8) 42 yellow green G* 160 (15) 43 blue51 80 (8) 42 yellow light green G* 20 (15) 43 blue52 80 (8) 42 yellow olive G* 20 (14) 44 blue green53 60 (9) 33 orange maroon G* 10 (14) 44 blue54 60 (9) 33 orange light G* 80 (15) 43 blue brown55 20 (8) 42 yellow brown 40 (9) 33 orange G* 40 (14) 44 blue56 10 (8) 42 yellow dark brown 40 (9) 43 orange G* 50 (14) 44 blue57 5 (9) 43 orange violet-blue 5 (10) 45 ruby G* 80 (14) 44 blue58 10 (9) 43 orange navy blue G* 80 (14) 44 blue59 20 (9) 43 orange dark navy blue G* 80 (14) 44 blue60 80 (8) 42 yellow black 40 (9) 43 orange G* 140 (14) 44 blue61 50 (16) 43 yellow yellow62 50 (17) 41 yellow yellow63 50 (18) 39 yellow yellow64 50 (19) 45 yellow yellow65 50 (20) 42 yellow yellow66 50 (21) 36 yellow yellow67 50 (22) 46 yellow yellow68 50 (23) 42 scarlet scarlet69 50 (24) 43 violet violet70 50 (25) 44 yellow yellow______________________________________ G* = mixture EXAMPLES 71 TO 386
Intermediate paper carriers are printed, in the gravure-printing process, firstly in places with the following reserve printing paste (A), and subsequently, without intermediate drying, over the whole surface with the following printing paste (B) for printing the base, the applied amount for each of the two printing pastes (A) and (B) being 10 to 12 g of paste per square meter of paper. After being printed with the two pastes (A) and (B), the intermediate carriers are dried at 100.degree. C. for 10 seconds. The carriers obtained are storage-stable and fast to rubbing.
Reserve printing paste A
200 parts of hexamethylolmelaminehexamethyl ether (commercial product consisting of hexamethylolmelamine which is etherified to the extent of 90 to 98% with methanol) as reserving agent (a),
35 parts of an ammonium polyacrylate (15%) as synthetic thickener (b.sub.1), and
optionally at least one dye according to the following Tables III to VII, as non-reservable dye (c).
Paste A is made up with water to 1000 parts.
Printing paste B for printing the base (background)
either 35 parts of an ammonium polyacrylate (15%) as synthetic thickener (b.sub.1) or 450 parts of sodium alginate (10%) as natural thickener (b.sub.2), and
at least one dye according to the following Tables III to VII, as reservable dye (g).
Fabrics made from the fibres listed in the following are printed with the intermediate carriers in the transfer printing process, the individual fabrics being pressed together with the respective intermediate carriers for 30 seconds in an ironing press under an excess pressure of 0.04 to 0.06 bar. There are obtained on the respective fabrics the patterns given in the following Tables III to VII, the patterns having sharp contours, that is to say, without aureoles.
Fibre materials
polyester fabric, weight per unit area 50-200 g/m.sup.2 (Table III),
fabric made from modified polyamide, weight 50-200 g/m.sup.2 (Table IV),
fabric made from cellulose triacetate, weight 50-200 g/m.sup.2 (Table V),
polyamide fabric, weight 50-200 g/m.sup.2 (Table VI), and
polyacrylonitrile fabric, weight 50-200 g/m.sup.2 (Table VII).
TABLE III__________________________________________________________________________ (polyester) Printing paste for printing the baseDye in reserve printing paste (application to whole surface)Ex- (application in places) dye Patterns obtainedample amount for- content amount content colour colour ofNo. parts mula % colour parts formula % colour thickener the pattern the__________________________________________________________________________ base71 0 -- -- -- 20 (9) 43 orange b.sub.1 silver navy blue G* 80 (14) 44 blue72 0 -- -- -- 40 (21) 36 yellow light yellow black 40 (9) 43 orange G* 120 (14) 44 blue73 50 (1) 48 yellow 60 (9) 43 orange b.sub.1 yellow orange74 50 (1) 48 yellow 40 (10) 45 ruby b.sub.1 yellow ruby75 50 (1) 48 yellow 80 (11) 33 brilliant b.sub.2 yellow pink pink76 50 (1) 48 yellow 60 (13) 42 violet b.sub.2 yellow violet77 50 (1) 48 yellow 80 (14) 44 blue b.sub.1 olive-green blue78 50 (1) 48 yellow 120 (15) 43 brilliant b.sub.2 light green light blue blue79 50 (1) 48 yellow 40 (21) 36 yellow b.sub.2 light green black 40 (9) 43 orange G* 120 (14) 44 blue80 100 (2) 54 red 80 (8) 42 yellow b.sub.2 red golden yellow81 100 (2) 54 red 40 (21) 36 yellow b.sub.2 red yellow82 100 (2) 54 red 40 (10) 45 ruby b.sub.1 light red ruby83 100 (2) 54 red 80 (12) 41 red b.sub.1 light red claret84 100 (2) 54 red 80 (14) 44 blue b.sub.1 red blue brilliant85 100 (2) 54 red 120 (15) 43 blue b.sub.2 red light blue86 100 (2) 54 red 20 (9) 43 orange b.sub.1 red navy blue G* 80 (14) 44 blue87 100 (2) 54 red 40 (21) 36 yellow b.sub.2 red black 40 (9) 43 orange G* 120 (14) 44 blue golden88 100 (3) 40 blue 80 (8) 42 yellow b.sub.2 dark blue yellow89 100 (3) 40 blue 40 (21) 36 yellow b.sub.2 dark blue yellow90 100 (3) 40 blue 60 (9) 43 orange b.sub.1 dark blue orange91 100 (3) 40 blue 80 (11) 33 brilliant b.sub.2 blue pink pink92 100 (3) 40 blue 80 (12) 41 red b.sub.1 blue claret brilliant93 100 (3) 40 blue 120 (15) 43 blue b.sub.2 dark blue light blue94 100 (3) 40 blue 20 (9) 43 orange b.sub.1 dark blue navy blue G* 80 (14) 44 blue95 100 (3) 40 blue 80 (8) 42 yellow b.sub.2 dark blue black 45 (9) 43 orange G* 135 (14) 44 blue96 100 (3) 40 blue 40 (21) 36 yellow b.sub.2 dark blue black 40 (9) 43 orange G* 120 (14) 44 blue97 60 (4) 48 blue 80 (8) 42 yellow b.sub.2 blue golden yellow98 60 (4) 48 blue 40 (21) 36 yellow b.sub.2 blue yellow99 60 (4) 48 blue 60 (9) 43 orange b.sub.1 blue orange100 60 (4) 48 blue 40 (10) 45 rubin b.sub.1 blue ruby101 60 (4) 48 blue 80 (11) 33 brilliant b.sub.2 blue pink pink102 60 (4) 48 blue 80 (12) 41 red b.sub.1 blue claret103 60 (4) 48 blue 60 (13) 42 violet b.sub.2 blue violet104 60 (4) 48 blue 80 (14) 44 blue b.sub.1 light blue dark blue105 60 (4) 48 blue 120 (15) 43 brilliant b.sub.2 dark blue light blue blue106 60 (4) 48 blue 20 (9) 43 orange b.sub.1 blue navy blue G* 80 (14) 44 blue107 60 (4) 48 blue 40 (21) 36 yellow b.sub.2 blue black 40 (9) 43 orange G* 120 (14) 44 blue108 100 (5) 32 turquoise 80 (8) 42 yellow b.sub.2 light blue golden yellow109 100 (5) 32 turquoise 40 (21) 36 yellow b.sub.2 light blue yellow110 100 (5) 32 turquoise 60 (9) 43 orange b.sub.1 blue-green orange111 100 (5) 32 turquoise 40 (10) 45 ruby b.sub.1 blue ruby112 100 (5) 32 turquoise 80 (11) 33 brilliant b.sub.2 blue pink pink113 100 (5) 32 turquoise 80 (12) 41 red b.sub.1 blue claret114 100 (5) 32 turquoise 60 (13) 42 violet b.sub.2 blue-green violet115 100 (5) 32 turquoise 80 (14) 44 blue b.sub.1 light-blue dark blue116 100 (5) 32 turquoise 120 (15) 43 brilliant b.sub.2 blue-green light blue blue117 100 (5) 32 turquoise 20 (9) 43 orange b.sub.1 light blue navy blue G* 80 (14) 44 blue118 100 (5) 32 turquoise 80 (8) 42 yellow b.sub.2 blue-green black 45 (9) 43 orange G* 135 (14) 44 blue119 100 (5) 32 turquoise 40 (21) 36 yellow b.sub.2 blue-green black 40 (9) 43 orange G* 120 (14) 44 blue 50 (1) 48120 10 (4) 48 yellow G* 80 (8) 42 yellow b.sub.2 green golden yellow blue121 50 (1) 48 yellow 40 (21) 36 yellow b.sub.2 green yellow G* 10 (4) 48 blue122 50 (1) 48 yellow 60 (9) 43 orange b.sub.1 green orange G* 10 (4) 48 blue123 50 (1) 48 yellow 40 (10) 45 ruby b.sub.1 green ruby G* 10 (4) 48 blue124 50 (1) 48 yellow 80 (12) 41 red b.sub.1 green claret G* 10 (4) 48 blue125 50 (1) 48 yellow 60 (13) 42 violet b.sub.2 green violet G* 10 (4) 48 blue126 50 (1) 48 yellow 80 (14) 44 blue b.sub.1 green dark blue G* 10 (4) 48 blue127 50 (1) 48 yellow 80 (8) 42 yellow b.sub.2 green black G* 45 (9) 43 orange G* 10 (4) 48 blue 135 (14) 43 blue128 50 (1) 48 yellow 40 (21) 36 yellow b.sub.2 green black G* 40 (9) 43 orange G* 10 (4) 48 blue 120 (14) 44 blue__________________________________________________________________________ G* = mixture
TABLE IV__________________________________________________________________________(modified polyamide) Printing paste for printing the baseDye in reserve printing paste (application to whole surface)Ex- (application in places) Dye Patterns obtainedample amount for- content amount for- content colour of colour ofNo. parts mula % colour parts mula % colour thickener the pattern the__________________________________________________________________________ base129 0 -- -- -- 100 (8) 42 yellow b.sub.2 white yellow130 0 -- -- -- 50 (21) 36 yellow b.sub.2 white golden yellow131 0 -- -- -- 50 (9) 43 orange b.sub.1 light yellow orange132 0 -- -- -- 40 (10) 45 ruby b.sub.1 light red ruby133 0 -- -- -- 100 (11) 33 brilliant b.sub.2 white pink pink134 0 -- -- -- 80 (12) 41 red b.sub.1 light red claret135 0 -- -- -- 60 (13) 42 violet b.sub.2 white violet136 0 -- -- -- 80 (14) 44 blue b.sub.1 light blue dark blue137 0 -- -- -- 120 (15) 43 brilliant b.sub.2 light olive light blue blue138 0 -- -- -- 15 (9) 43 orange G* b.sub.1 silver navy blue 85 (14) 44 blue139 0 -- -- -- 100 (8) 42 yellow b.sub.2 olive black 30 (9) 43 orange G* 140 (14) 44 blue140 0 -- -- -- 50 (21) 36 yellow b.sub.2 light grey black 30 (9) 43 orange G* 140 (14) 44 blue141 50 (1) 48 yellow 50 (9) 43 orange b.sub.1 yellow orange142 50 (1) 48 yellow 40 (10) 45 ruby b.sub.1 yellow ruby143 50 (1) 48 yellow 100 (11) 33 brilliant b.sub.2 yellow pink pink144 50 (1) 48 yellow 80 (12) 41 red b.sub.1 yellow claret145 50 (1) 48 yellow 60 (13) 42 violet b.sub.2 yellow violet146 50 (1) 48 yellow 80 (14) 44 blue b.sub.1 light green dark blue147 50 (1) 48 yellow 120 (15) 43 brilliant b.sub.2 light green light blue blue148 50 (1) 48 yellow 15 (9) 43 orange b.sub.1 light green navy blue G* 85 (14) 44 blue149 50 (1) 48 yellow 100 (8) 42 yellow b.sub.2 light green black 30 (9) 43 orange G* 40 (14) 44 blue150 50 (1) 48 yellow 50 (21) 36 yellow b.sub.2 light green black 30 (9) 43 orange G* 140 (14) 44 blue151 100 (2) 54 red 100 (8) 42 yellow b.sub.2 red yellow152 100 (2) 54 red 50 (21) 36 yellow b.sub.2 red yellow153 100 (2) 54 red as Examples 142 and 144 to 150 as Examples 82, 83, 12to and 84 to 87160161 100 (3) 40 blue as Examples 150, 152, 141 to 144 as Examples 88, 89, 90,to 147 to 150 8 and 91 to 96. -170171 60 (4) 48 blue as Examples 151, 152 and 141 to as Examples 97 to 106,to 31 and 107182183 100 (5) 32 turquoise as Examples 151, 152, 141 to 146 as Examples 108 to 115to 148 to 150 and 117 to 119193194 50 (1) 48 yellow as Examples 151, 152 and 141 to as Examples 120 to 123,to G* 9. 124 to 126, 16, 28,205 10 (4) 48 blue 127 and__________________________________________________________________________ 128 G = mixture
TABLE V__________________________________________________________________________(Cellulose triacetate) Printing paste for printing the baseDye in reserve printing paste (application to whole surface)Ex- (application in places) dye Patterns obtainedample amount content amount content colour colour ofNo. parts formula % colour parts formula % colour thickener the pattern the__________________________________________________________________________ base206 0 -- -- -- as Examples 129 to 140 as Examples 129 to 140to217218 50 (1) 48 yellow as Examples 141 to 150 as Examples 141 to 150to217228 100 (2) 54 red as Examples 151, 152, 142 and 144 as Examples 151, 152,to 150 82, 83, 12 and 84 to 87238239 100 (3) 40 blue as Examples 151, 152, 141 to 144 and as Examples 86, 89, 90,to 8, 91, 92 and 93245246 60 (4) 48 blue as Examples 151, 152 and 141 to as Examples 97 to 106,to 31 and 107257258 100 (5) 32 turquoise as Examples 151, 152 and 141 to as Examples 108 to 119to269270 50 (1) 48 yellow as Examples 151, 152 and 141 to as Examples 120 to 123,to G* 9, 124 to 126, 16, 28,281 10 (4) 48 blue 127 and__________________________________________________________________________ 128 G* = mixture
TABLE VI__________________________________________________________________________(polyamide) Printing paste for printing the baseDye in reserve printing paste (application to whole surface)(application in places) Dye Patterns obtainedEx. amount for- content amount for- content colour colour ofNo. parts mula % colour parts mula % colour thickener the pattern the__________________________________________________________________________ base282 0 -- -- -- 40 (21) 36 yellow b.sub.2 white yellow283 0 -- -- -- 80 (25) 44 golden b.sub.2 light golden yellow yellow284 0 -- -- -- 150 (11) 33 brilliant b.sub.2 pink red pink285 0 -- -- -- 100 (14) 44 blue b.sub.1 light dark blue286 0 -- -- -- 120 (15) 43 brilliant b.sub.2 white light blue blue287 0 -- -- -- 20 (21) 36 yellow b.sub.2 light navy blue 30 (11) 33 brilliant G* 90 (14) 44 pink b.sub.2 blue288 0 -- -- -- 40 (21) 36 yellow b.sub.2 olive- black 20 (25) 44 golden yellow 50 (11) 33 yellow G* 130 (14) 44 brilliant pink blue289 80 (1) 48 yellow as Examples 283 to 288 yellow as Examplesto green 283 to 288294295 100 (6) 49 yellow as Examples 283 to 288 yellow as Examplesto green 283 to 288300301 100 (2) 54 red as Examples 282, 283 and 285 to 288 red as Examplesto 282, 283 and306 285 to 288307 200 (7) 31 red as Examples 284 to 288 light as Examplesto 284 to 288311312 100 (3) 40 blue as Examples 282 to 285 blue as Examplesto 282 to 285315316 80 (4) 48 blue as Examples 284, 285, 287 and 288 blue as Examplesto 284, 285,319 287 and 288320 120 (5) 32 turquoise as Examples 282 to 285, 287 and 288 blue-green as Examplesto 282 to 285,325 287 and 288326 50 (1) 48 yellow as Examples 282 to 288 green as Examplesto G* 282 to 288322 10 (4) 48 blue__________________________________________________________________________ G* = mixture
TABLE VII__________________________________________________________________________(polyacrylonitrile) Printing paste for printing the baseDye in reserve printing paste (application to whole surface)Ex- (application in places) Dye Patterns obtainedample amount content amount content colour colour ofNo. parts formula % colour parts formula % colour thickener the pattern the__________________________________________________________________________ base333 0 -- -- -- 80 (9) 43 orange b.sub.1 light brown orange-brown334 0 -- -- -- 100 (11) 33 brilliant b.sub.2 light grey light red pink335 0 -- -- -- 50 (12) 41 red b.sub.1 light grey light violet336 0 -- -- -- 70 (13) 42 violet b.sub.2 light grey dark violet337 0 -- -- -- 100 (14) 44 blue b.sub.1 light yellow blue338 0 -- -- -- 120 (15) 43 brilliant b.sub.2 light yellow light blue blue339 0 -- -- -- 40 (9) 43 orange b.sub.1 grey navy blue G* 120 (14) 44 blue340 0 -- -- -- 110 (8) 42 yellow b.sub.2 light yellow black 35 (9) 43 orange 20 (13) 42 violet G* 135 (14) 44 blue341 0 -- -- -- 35 (21) 36 yellow light yellow black 30 (9) 43 orange 15 (13) 42 violet G* 150 (14) 44 blue342 80 (1) 48 yellow as Examples 333 to 341 yellow as Examplesto green 333 to 341350351 100 (6) 49 yellow as Examples 333 to 341 yellow as Examplesto green 333 to 341359360 250 (7) 31 red 100 (8) 42 yellow b.sub.2 red yellow361 250 (7) 31 red 50 (21) 36 yellow b.sub.2 red yellow362 250 (7) 31 red as Examples 335 to 341 red as Examplesto 335 to 341368369 80 (4) 48 blue as Examples 360, 361, 333 to 336 and blue as Examplesto 339 to 341 360, 361, 333377 to 336 and 339 to 341378 85 (6) 49 yellow as Examples 333 to 341 green as Examplesto 333 to 341386 15 (4) 48 blue__________________________________________________________________________ G* = mixture
EXAMPLES 387 TO 402
Intermediate carriers made of paper are printed, in the gravure printing process, firstly in places with one of the following reserve printing inks (A) to (D), and subsequently, without intermediate drying, over the whole surface with one of the following inks (E) to (H) for printing the base, the deposited amount for each of the employed inks being 8 to 10 g of ink per square meter of paper. The intermediate carriers are thereupon dried at 100.degree. C. for 10 seconds. They are storage-stable and fast to rubbing.
Reserve printing ink A
200 parts of hexamethylolmelaminehexamethyl ether (commercial product),
78 parts of cellulose acetopropionate,
20 parts of 2-amino-2-methyl-propanol hydrochloride,
312 parts of isopropanol,
312 parts of n-propanol, and
78 parts of water.
Reserve printing ink B
150 parts of hexamethylolmelaminehexamethyl ether (commercial product),
78 parts of cellulose acetopropionate,
50 parts of the non-reservable yellow dye of the formula (I) (48%),
15 parts of 2-amino-2-methyl-propanol hydrochloride,
315 parts of isopropanol,
315 parts of n-propanol, and
78 parts of water.
Reserve printing ink C
150 parts of hexamethylolmelaminehexamethyl ether (commercial product),
74 parts of cellulose acetopropionate,
100 parts of the non-reservable red dye of the formula (2) (54%),
15 parts of 2-amino-2-methyl-propanol hydrochloride,
294 parts of isopropanol,
294 parts of n-propanol, and
74 parts of water.
Reserve printing ink D
150 parts of hexamethylolmelaminehexamethyl ether (commercial product),
77 parts of cellulose acetopropionate,
60 parts of the non-reservable blue dye of the formula (4) (48%),
15 parts of 2-amino-2-methyl-propanol hydrochloride,
310 parts of isopropanol,
310 parts of n-propanol, and
77 parts of water.
Ink E for printing the base
91 parts of cellulose acetopropionate,
90 parts of the reservable, orange-coloured dye of the formula (9) (43%),
364 parts of isopropanol,
364 parts of n-propanol, and
91 parts of water.
Ink F for printing the base
88 parts of cellulose acetopropionate,
120 parts of the reservable red dye of the formula (12) (41%),
352 parts of isopropanol,
352 parts of n-propanol, and
88 parts of water.
Ink G for printing the base
As ink F, but with replacement of 120 parts of the dye of the formula (12) by 120 parts of the reservable blue dye the formula (14) (44%).
Ink H for printing the base
62 parts of cellulose acetopropionate,
120 parts of the reservable yellow dye of the formula (8) (42%),
65 parts of the reservable orange-coloured dye of the formula (9) (43%),
200 parts of the reservable blue dye of the formula (14) (44%),
246 parts of isopropanol,
246 parts of n-propanol, and
62 parts of water.
Fabrics made from polyester (weight 100 g/m.sup.2) are printed with the intermediate carriers by the transfer printing process, the individual fabrics being pressed together with the respective intermediate carriers for 30 seconds in an ironing press with an excess pressure of 0.04 to 0.06 bar. There are obtained on the respective fabrics the patterns given in the following Table VIII, the patterns having sharp contours, that is to say, being without aureoles.
TABLE VIII______________________________________ Printing ink for dyeing Reserve prin- the base ting ink (applicationEx- (application to whole sur- Patterns obtainedample in places) face) desig- Colour of the Colour ofNo. designation nation pattern the base______________________________________387 A E light yellow orange388 A F pink violet389 A G light blue dark blue390 A H silver-grey black391 B E yellow orange392 B F yellow violet393 B G green dark blue394 B H green-yellow black395 C E red orange396 C F red violet397 C G red dark blue398 C H red black399 D E green orange400 D F dark blue violet401 D G light blue dark blue402 D H blue-green black______________________________________
EXAMPLES 403 TO 418
The procedure is carried out as described in Examples 387 to 402, the intermediate carriers being printed however with the following inks.
Ink A
200 parts of hexamethylolmelamine-hexamethyl ether,
62 parts of carboxymethyl cellulose,
20 parts of 2-amino-2-methyl-propanol hydrochloride,
562 parts of ethanol,
140 parts of ethyl acetate, and
16 parts of ethylene glycol.
Ink B
150 parts of hexamethylolmelaminehexamethyl ether,
63 parts of carboxymethyl cellulose,
50 parts of the dye of the formula (1) (48%),
15 parts of 2-amino-2-methyl-propanol hydrochloride,
566 parts of ethanol,
141 parts of ethyl acetate, and
15 parts of ethylene glycol.
Ink C
150 parts of hexamethylolmelaminehexamethyl ether,
58 parts of carboxymethyl cellulose,
100 parts of the dye of the formula (2) (54%),
15 parts of 2-amino-2-methyl-propanol hydrochloride,
530 parts of ethanol,
132 parts of ethyl acetate, and
15 parts of ethylene glycol.
Ink D
150 parts of hexamethylolmelaminehexamethyl ether,
62 parts of carboxymethyl cellulose,
60 parts of the dye of the formula (4) (48%),
15 parts of 2-amino-2-methyl-propanol hydrochloride,
558 parts of ethanol,
140 parts of ethyl acetate, and
15 parts of ethylene glycol.
Ink E
73 parts of carboxymethyl cellulose,
90 parts of the dye of the formula (9) (43%),
656 parts of ethanol,
163 parts of ethyl acetate, and
18 parts of ethylene glycol.
Ink F
70 parts of carboxymethyl cellulose,
120 parts of the dye of the formula (12) (41%),
634 parts of ethanol,
158 parts of ethyl acetate, and
18 parts of ethylene glycol.
Ink G
As in the case of ink F, but with replacement of 120 parts of the dye of the formula (12) by 120 parts of the dye of the formula (14) (44%).
Ink H
49 parts of carboxymethyl cellulose,
120 parts of the dye of the formula (8) (42%),
65 parts of the dye of the formula (9) (43%),
200 parts of the dye of the formula (14) (44%),
443 parts of ethanol,
111 parts of ethyl acetate, and
12 parts of ethylene glycol.
The intermediate carriers obtained are storage-stable and fast to rubbing.
Polyester fabrics are printed, in the manner given in Examples 387 to 402, with the combinations of inks A to H according to the following Table IX.
TABLE IX______________________________________Example Reserve printing Ink for printing the baseNo. ink designation designation______________________________________403 A E404 A F405 A G406 A H407 B E408 B F409 B G410 B H411 C E412 C F413 C G414 C H415 D E416 D F417 D G418 D H______________________________________
There are obtained in these tests patterns having sharp contours, that is to say, without aureoles, the colours of the patterns corresponding to the colours given in Table VIII.
EXAMPLES 419 TO 434
The procedure is carried out in the manner described in Examples 387 to 402, the intermediate carriers being printed however with the following inks:
Ink A
200 parts of hexamethylolmelaminehexamethyl ether,
23 parts of hydroxypropyl cellulose,
20 parts of 2-amino-2-methyl-propanol hydrochloride,
507 parts of ethanol, and
250 parts of water.
Ink B
150 parts of hexamethylolmelaminehexamethyl ether,
24 parts of hydroxypropyl cellulose,
50 parts of the dye of the formula (1) (48%),
15 parts of 2-amino-2-methyl-propanol hydrochloride,
510 parts of ethanol, and
251 parts of water.
Ink C
150 parts of hexamethylolmelaminehexamethyl ether,
22 parts of hydroxypropyl cellulose,
100 parts of the dye of the formula (2) (54%),
15 parts of 2-amino-2-methyl-propanol hydrochloride,
478 parts of ethanol, and
235 parts of water.
Ink D
150 parts of hexamethylolmelaminehexamethyl ether,
23 parts of hydroxypropyl cellulose,
60 parts of the dye of the formula (4) (48%),
15 parts of 2-amino-2-methyl-propanol hydrochloride,
504 parts of ethanol, and
248 parts of water.
Ink E
27 parts of hydroxypropyl cellulose,
90 parts of the dye of the formula (9) (43%),
592 parts of ethanol, and
291 parts of water.
Ink F
26 parts of hydroxypropyl cellulose,
120 parts of the dye of the formula (12) (41%),
572 parts of ethanol, and
282 parts of water.
Ink G
As ink F, but with the replacement of 120 parts of the dye of the formula (12) by 120 parts of the dye of the formula (14) (44%).
Ink H
18 parts of hydroxypropyl cellulose,
120 parts of the dye of the formula (8) (42%),
65 parts of the dye of the formula (9) (43%),
200 parts of the dye of the formula (14) (44%),
400 parts of ethanol, and
197 parts of water.
The intermediate carriers obtained are storage-stable and fast to rubbing.
Polyester fabrics are printed as given in Examples 387 to 402 with the combinations of the inks A to H according to the following Table X:
TABLE X______________________________________Example Reserve printing Ink for printing the baseNo. ink designation designation______________________________________419 A E420 A F421 A G422 A H423 B E424 B F425 B G426 B H427 C E428 C F429 C G430 C H431 D E432 D F433 D G434 D H______________________________________
There are obtained in these tests patterns having sharp contours, that is to say, without aureoles, the colours of the patterns corresponding to the colours given in Table VIII.

Number	Name	Date	Kind
3813218	de Plasse	May 1974
4171202	Sideman et al.	Oct 1979

Number	Date	Country
2755730	Jun 1978	DEX
2758398	Jul 1978	DEX
5055412	May 1975	JPX
569141	Nov 1975	CHX
1243223	Aug 1971	GBX

Thermotransfer process for printing synthetic fibre materials with multi-color effects, and carrier for performing the process

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