EP0045479B1 - Transfer printing sheet, process for its preparation and its use - Google Patents

Description

in welcher X ein Wasserstoff- oder Halogenatom, R, R₁ und R₂ je eine Alkylgruppe von 1 bis 4 Kohlenstoffatomen, und R₃ ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen bedeuten, mit dem orangefarbenen Dispersionsfarbstoff der Formel

enthält.The invention relates to transfer printing media which are characterized in that they are impregnated or printed with a preparation which is a mixture of a blue, slightly subliming disperse dye of the general formula I.

in which X represents a hydrogen or halogen atom, R, R ₁ and R ₂ each represent an alkyl group of 1 to 4 carbon atoms, and R _{3 represents} a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, with the orange-colored disperse dye of the formula

contains.

With these transfer printing media you get strong and real black colors when thermal transfer printing on polyester and polyester mixed materials.

in welcher Y ein Wasserstoff- oder Halogenatom ist, R₄ für eine Methoxy- oder Ethoxygruppe steht, oder, wenn Y ein Chlor- oder Bromatom ist, auch für ein Wasserstoffatom oder eine Methylgruppe steht, R_s eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen ist, R₆ ein Wasserstoffatom ist oder die Bedeutung von R₅ hat und R₇ eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen bedeutet, beispielsweiseden Farbstoff der Formel

oder zusätzlich einen blauen, leicht sublimierenden Anthrachinon-Farbstoff, wie beispielsweise die Dispersionsfarbstoffe C. I. Disperse Blue, 3, 7, 14, 19 und 26, oder zusätzlich den gelben Farbstoff der Formel

enthalten.In addition to a blue dye of the above formula I, the preparations can additionally a blue, slightly subliming disperse dye of the general formula II

in which Y is a hydrogen or halogen atom, R _{4 represents} a methoxy or ethoxy group, or, if Y is a chlorine or bromine atom, also represents a hydrogen atom or a methyl group, R _{s is} an alkyl group having 1 to 4 carbon atoms , R _{6 is} a hydrogen atom or has the meaning of R ₅ and R _{7 represents} an alkyl group having 1 to 4 carbon atoms, for example the dye of the formula

or additionally a blue, slightly subliming anthraquinone dye, such as, for example, the disperse dyes CI Disperse Blue, 3, 7, 14, 19 and 26, or additionally the yellow dye of the formula

contain.

The invention further relates to a process for the production of these transfer printing carriers, which is characterized in that the carrier material is impregnated or printed with the preparations mentioned above. The invention further relates to the use of these supports for dyeing and printing sheet-like structures by the thermal transfer printing process.

• Die Azofarbstoffe der vorstehend genannten Formeln und II sind bekannt und nach den für solche Farbstoffe üblichen Methoden herstellbar.

Preferred embodiments of the invention are explained in more detail below:

• The azo dyes of the above formulas and II are known and can be prepared by the methods customary for such dyes.

Slightly subliming dyes are to be understood in all cases as substances which sublimate at least 60% without decomposition at atmospheric pressure between 150 and 220 ° C.

In the combinations of dyes used according to the invention, the blue dyes are always the main constituent; if blue dyes other than those of formula 1 are used, the dye of the formula is usually present in at least 10, preferably 50%, based on the weight of all blue dyes.

The dye combinations according to the present invention are distinguished by a number of advantages over known black mixtures. As a result of the good rheological properties, easy-to-pour, low-electrolyte and low-dispersant formulations can be produced with a high dye concentration, which are particularly sought after as printing pastes for printing on paper, since only small amounts of printing paste are required. The blends also show excellent transfer behavior and deliver color-deep prints with a sharp print image. The high light-fastness of the black colorations obtained, which exceeds that of the blue components of the formula I, is particularly surprising.

As is known, all sheet-like structures which are inert to the dyes applied and which do not hinder sublimation are suitable as carrier material for the transfer printing supports according to the invention. Sheet structures made of metal, such as aluminum foil, or of natural or regenerated cellulose materials, such as foils, woven fabrics, knitted fabrics or preferably paper webs, are suitable.

The formulations which contain the dye mixtures and with which the carrier materials are impregnated or printed can be aqueous printing pastes, as are customary in textile printing, or organic printing inks, as are used in graphic printing.

Aqueous printing inks contain the usual natural or synthetic thickeners, for example polyvinyl alcohols, methylcelulose or polymerization products containing carboxy groups, for example polyacrylates.

The composition of the organic printing inks depends on the type of substrate, the substrate, the printing process and the equipment available. In general, such printing inks consist of the dye mixtures described above, a binder, one or more dispersants and, if appropriate, solvents, fillers and preservatives.

Suitable binders are natural, semi-synthetic and synthetic resins, i.e. H. Polymerization, polycondensation and polyaddition products. Examples of suitable resins are: rosin and its derivatives, maleinate resins, oil-free alkyd resins, alkyd resins made from synthetic and natural fatty acids and arylated alkyd resins. Terpene resins, polyvinyl resins such as polyvinyl acetate and polyvinyl chloride, copolymers and graft polymers with various vinyl monomers, acrylate resins, naphthalene-formaldehyde resins, ketone resins, silicone resins and cellulose derivatives such as cellulose esters, for example nitrocellulose or cellulose acetate, and cellulose ethers, such as, for example, methyl cellulose polysaccharide and others, are also suitable.

Nonionic and anionogenic products are preferably used as dispersants. Examples of nonionic products are: addition products of alkylene oxide with fatty acids, fatty alcohol polyglycol ethers, phenol and alkylphenol polyglycol ethers, but also oxalkylates of fatty acids esterified with polyhydric alcohols or of resin derivatives such as hydroabietyl alcohol. Suitable anionic dispersants are: naphthalenesulfonic acid-formaldehyde condensates, ligninsulfonates and sulfite waste products.

The type of solvent depends on the type of printing process. Esters, ketones or alcohols, for example butyl acetate, acetone, methyl ethyl ketone, ethanol, isopropanol or butanol, are particularly preferred.

The preparations (printing inks) discussed here can either be obtained by mixing and adjusting preparations of the individual dyes. However, the procedure can also be such that presscake of the individual dyes required for the dye mixture is combined, ground with the addition of suitable dispersants, so that at least 90% of the dispersed particles are less than 3 μm, and adjusted to the desired dye content.

The printing inks can be printed using all common printing methods, i.e. high, flat, gravure or screen printing. Rotogravure and rotary film printing are particularly suitable printing processes for the production of printed paper auxiliary substrates.

Suitable substrates are sheet-like structures such as nonwovens, felts, furs, carpets, foils and, above all, woven and knitted fabrics made from synthetic or partially synthetic materials, in particular from aromatic polyesters such as polyethylene glycol terephthalate or cellulose acetates such as cellulose triace tat and cellulose-2 1/2 acetate or polyamides. These synthetic or semi-synthetic materials show an affinity for the dye mixtures. However, it is also possible to dye and print other substrates after thermal transfer printing, which in themselves have no affinity for these dyes, namely by preparing such substrates with the synthetic or partially synthetic materials mentioned, for example with an appropriate coating of such plastics envelops. It is also possible to treat natural fiber materials, which have no affinity for the dye mixtures, with suitable preparations and thus to make these substances affine to these dyes. Corresponding methods are known for example from DE-C-2 551 410, DE-B-2 436 783 or DE-A-2 045 465.

Thermal transfer printing is generally known and is described in detail, for example, in FR-A-1 223 330, 1 334829 and 1 585119. Here, the auxiliary carriers, which are impregnated or printed with the suitable preparations, are brought into close contact with the substrate to be colored or printed, whereupon the dye is transferred from the carrier to the substrate and fixed there under the action of heat and, if appropriate, pressure or vacuum .

With the above dye mixtures, when used in accordance with the invention (transfer printing) on the substrates, black, strongly colored dyeings and prints with good fastness properties are obtained. If the above dye mixtures are finished in accordance with the conditions customary for disperse dyes, then with such an adjustment strong black dyeings with good fastness properties are obtained even after the conventional dyeing process on polyester materials.

zur Anwendung. Gegenüber diesem bekannten Orangefarbstoff zeichnet sich der zwingend in Kombination mit einem blauen Dispersionsfarbstoff der Formel I erfindungsgemäß angewandte Orangefarbstoff der Formel

durch eine wesentlich bessere Lichtechtheit beim Färben von Polyestergewebe aus, was im Hinblick auf die Strukturähnlichkeit der beiden Orangefarbstoffe als überraschend zu erachten ist.JP-A-77136 275 describes a process for printing molded structures made of polyester by the thermal transfer printing process, using monoazo dyes of a certain general formula. According to Example 5 of this laid-open specification, a mixture of a disperse dye which falls under the general formula I of claim 1 of the present invention comes in combination with, inter alia, the orange dye of the formula

to use. Compared to this known orange dye, the orange dye of the formula used in accordance with the invention in combination with a blue disperse dye of the formula I is distinguished

due to a much better lightfastness when dyeing polyester fabric, which is surprising in view of the structural similarity of the two orange dyes.

The invention is explained in more detail in the following examples. Unless otherwise stated, details of parts and percentages relate to the weight.

• 300 Teile des trockenen Farbstoffs werden mit einer Lösung, bestehend aus 40 Teilen eines Diessigsäureesters eines Propylen-Ethylenoxid-Addukts mit einem mittleren Molgewicht von 8 500 und einem Ethylenoxidanteil von 80 %, 20 Teilen eines Sulfobernsteinsäurehalbesters eines oxethylierten Kondensationsprodukts aus Nonylphenol und Formaldehyd (DE-C-2132403, Beispiel B), 120 Teilen Ethylenglykol, 2 Teilen Chloracetamid als Konservierungsmittel und 350 Teilen Wasser in einer Perlmühle mit Siliquarzitperlen gemahlen. Nach 5 Stunden erhält man eine Dispersion, deren Teilchen zu über 90 % kleiner als 3 !J.m sind. Nach Zugabe von 180 Teilen Wasser und Abtrennen der Perlen erhält man 1 000 Teile eines gut fließfähigen, 30 %igen Farbstoffteigs.

Unless stated otherwise, the settings of the dyes used in the examples contain 30% by weight of dye and were prepared as follows:

• 300 parts of the dry dye are mixed with a solution consisting of 40 parts of a diacetic acid ester of a propylene-ethylene oxide adduct with an average molecular weight of 8,500 and an ethylene oxide content of 80%, 20 parts of a sulfosuccinic acid semiester of an oxyethylated condensation product of nonylphenol and formaldehyde (DE- C-2132403, Example B), 120 parts of ethylene glycol, 2 parts of chloroacetamide as a preservative and 350 parts of water in a bead mill with silica quartz beads. After 5 hours, a dispersion is obtained, the particles of which are more than 90% smaller than 3 μm. After adding 180 parts of water and separating the beads, 1,000 parts of a readily flowable, 30% dye paste are obtained.

• Farbstoffe der Formel I
  
  

The numbers indicate the following dyes:

• Dyes of the formula I.
  
  

Other dyes:

example 1

400 parts of a setting of the blue dye (1) and 140 parts of a setting of the orange dye (12) are stirred with a high-speed stirrer for 30 minutes until a homogeneous, streak-free mixture is obtained. Due to the special form of preparation of the individual components and the predominantly nonionic dispersant, lightfast, extremely strong black prints on polyester and polyester blended fabrics are obtained both after transfer printing from conventional petrol emulsions and with synthetic thickening.

Example 2

If 400 parts of a setting containing dye (1), 140 parts of the setting of the dye (12) are mixed with 20 parts of a 45% setting of the yellow dye (11), then one also achieves, after stocking, with thickened stock on paper, after the transfer Polyester or polyester blended fabrics with excellent color, black prints with good fastness properties.

Example 3

200 parts of a setting of the blue dye (1), 200 parts of a setting of the blue dye (9) and 140 parts of a setting of the orange dye (12) are stirred with a high-speed stirrer for 30 minutes until a homogeneous, streak-free mixture is obtained. Due to the special preparation form of the individual components and the predominantly nonionic dispersant, light-fast, extremely color-rich black prints on polyester and polyester blended fabrics are obtained both after transfer printing from conventional gasoline emulsions and with synthetic thickened stocks.

Example 4

200 parts of a setting of the blue dye (3), 200 parts of a setting of the blue dye (10) and 140 parts of a setting of the orange dye (12) are stirred with a high-speed stirrer for 30 minutes until a homogeneous mixture is obtained. Due to the special preparation form of the individual components and the predominantly nonionic dispersant, light-fast, extremely color-rich black prints on polyester and polyester blended fabrics are obtained both after transfer printing from conventional gasoline emulsions and with synthetic thickened stocks.

Example 5

425 parts of a setting of the blue dye (4) and 140 parts of a setting of the orange dye (12) are stirred with a high-speed stirrer for 30 minutes until a homogeneous, streak-free mixture is obtained. Due to the special preparation form of the individual components and the predominantly nonionic dispersant, light-fast, extremely color-rich black prints on polyester and polyester blended fabrics are obtained both after transfer printing from conventional gasoline emulsions and with synthetic thickened stocks.

Example 6

If you mix 370 parts of a setting of the dye (5), 130 parts of the setting of the dye (12) with 40 parts of a 45% setting of the yellow dye (11), you can also achieve this, with stock thickening on paper, after the transfer on polyester or polyester blended fabrics, extremely strong, black prints with good fastness properties.

Example 7

420 parts of a setting of the blue dye (6) and 140 parts of a setting of the orange dye (12) are stirred with a high-speed stirrer for 30 minutes until a homogeneous, streak-free mixture is obtained.

Due to the special form of preparation of the individual components and the predominantly non-ionic dispersant, light-fast, extremely strong black prints on polyester and polyester blended fabrics are obtained both after transfer printing from conventional petrol emulsions and with synthetic thickening.

Claims (10)

1. A transfer print carrier impregnated or printed with a composition comprising a mixture of a blue, easily sublimeable disperse dye of the general formula I

in which X is a hydrogen atom or halogen atom, R, R₁ and R₂ are each an alkyl group of 1 to 4 carbon atoms and R₃ is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, together with an orange disperse dye, wherein the orange disperse dye is the dye of the formula

2. A transfer print carrier as claimed in claim 1, wherein the dye composition additionally comprises a blue, easily sublimeable disperse dye of the general formula 11

in which Y is a hydrogen atom or halogen atom, R₄ is a methoxy or ethoxy group or, if Y is a chlorine atom or bromine atom, may also be a hydrogen atom or a methyl group, R₅ is an alkyl group of 1 to 4 carbon atoms, R₆ is a hydrogen atom or has the same meaning as R_s and R₇ is an alkyl group of 1 to 4 carbon atoms.

3. A transfer print carrier as claimed in claim 2, wherein the dye composition contains the dye of the formula

as the additional blue, easily sublimeable disperse dye of the said general formula 11.

4. A transfer print carrier as claimed in claim 1, wherein the dye composition additionally comprises a blue, easily sublimeable anthraquinone dye.

5. A transfer print carrier as claimed in claim 4, wherein the dye composition contains the dye of the formula

as the additional blue, easily sublimeable anthraquinone dye.

6. A transfer print carrier as claimed in claim 1, wherein the dye composition additionally comprises the yellow dye of the formula

7. A process for the preparation of a transfer print carrier as claimed in any of claims 1 to 6, by impregnating or printing the carrier material with a disperse dye composition, wherein the composition comprises a mixture of a blue, easily sublimeable disperse dye of the general formula (I) given in claim 1 with the orange disperse dye of the general formula given in claim 1, with or without the additional presence of a blue, easily sublimeable disperse dye of the general formula (II) given in claim 2 or of a blue, easily sublimeable anthraquinone dye or of the yellow dye of the formula given in claim 6.

8. Use of the transfer print carrier as claimed in any of claims 1 to 6 for dyeing or printing a sheet-like structure by the thermal-transfer printing process.

9. Use as claimed in claim 8 of the transfer print carrier as claimed in any of claims 1 to 6, wherein the sheet-like structure consists of or has been treated with a synthetic polymeric material.

10. Uses as claimed in claim 8, of the transfer print carrier as claimed in any of claims 1 to 6, wherein the sheet-like structure consists of or contains a natural fiber material and has been treated with a preparation which imparts to the said material an affinity for the dye mixtures referred to in any of claims 1 to 6.