EP0062183B1 - Resist printing process - Google Patents

Description

The invention relates to a new process for producing reserve prints on fiber materials consisting of cellulose or containing cellulose, which are printed or primed with a phenolic or enolic coupling component, by printing on a reserve which prevents the formation of a water-insoluble azo dye, followed by overprinting with a stabilized diazonium salt, washing out the soluble components and completion of the print in the usual way.

The process is characterized in that the reserve contains a pyrazolone derivative as a reservation agent.

Particular embodiments of the method according to the invention are the subject of the dependent claims 2 to 5.

The new printing process is particularly suitable for Rouleaux printing, rotary film printing and flat film printing.

Louis Diserens reports on the possibilities of using reserve agents which prevent the formation of insoluble azo stains in: "The latest advances in the use of dyes", first volume, Verlag Birkhäuser, Basel, 3rd edition 1951, p. 604 ff. As Reserve agents are listed as reducing agents, such as tin chloride, sulphurous acid salts or xanthates; the ammonium salt of phenylhydrazine sulfonic acid is also mentioned as a reserve. These reserve means do not allow, or only with severe restrictions, to achieve a color reserve print with reactive dyes under real dye salts printed on naphthol primers (Lit: Melliand, 1970, p. 215: "The coloristics of the ( ^R ) Remazol dyes").

From DE-A 2 104 065 a process for the production of colored reserves with reactive dyestuffs under diazo-real salts is also known, but reducing agents are also used which are known to have the undesirable effect of attacking the illuminating dyes to a greater or lesser extent.

A variant of the method according to the invention is characterized in that the cotton fabric to be printed is first prepared over the entire area with a naphthol or enol according to a known method or is printed in a pattern by printing on naphtholate or enolate printing paste. An aqueous printing paste containing the reserve and a reactive dye or the reserve and a mixture of several reactive dyes is applied to this dried naphthol impregnation by printing processes customary in textile printing. With this reserve printing paste, with or without intermediate drying, but preferably wet-on-wet, a printing paste containing a fast dye salt is overprinted and, after drying, the reactive dye is fixed by known methods. This is followed by an aqueous alkaline aftertreatment, as is customary in base printing. Color effects are thus obtained under overprinted, flat-colored patterns.

Another variant of the method according to the invention is designed in such a way that the printed-on reserve pastes are first dried with the reactive dye, the reactive dyes are fixed by a steaming process and then the goods are dyed on a padder or by another suitable device with an aqueous solution of a fast dye salt. In this case you get colorful reserve effects under a plain colored fund.

Suitable cellulose-containing fiber materials are in particular those which contain little polyacrylonitrile and / or little polyester mixed with cotton.

Fabrics made of pure cotton are very particularly preferably suitable for the process according to the invention.

Possible reactive dyes are those which have reactive groups which have one or more reactive groups or removable substituents which, when the dyes are applied to cellulose materials, are able to react with the hydroxyl groups of the cellulose in the presence of acid-binding agents and, if appropriate, to form covalent bonds . Such fiber-reactive groups are known from the literature in large numbers.

• Halogen (CI, Br oder F), Ammonium, einschließlich Hydrazinium, Sulfonium, Sulfonyl, Azido-(N₃), Rhodanido, Thio, Thiolether, Oxyether, Sulfinsäure und Sulfonsäure. Im einzelnen sind beispielsweise zu nennen:
  • Mono- oder Dihalogen-symmetrische-triazinylreste und Mono-, Di- oder Trihalogenpyrimidinylreste.

Suitable reactive groups which contain at least one detachable substituent attached to a heterocyclic or to an aliphatic radical include those which contain at least one reactive substituent attached to a 5- or 6-membered heterocyclic ring, such as a monazine or diazine ring. , Triazine, for example pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetrical or symmetrical triazine ring, or to such a ring system which has one or more fused aromatic rings, such as a quinoline or phthalazine , Chinnoline, quinazoline, quinoxaline, acridine, phenazine and phenanthridine ring system; the 5- or 6-membered heterocyclic rings which have at least one reactive substituent are accordingly preferably those which contain one or more nitrogen atoms and can contain 5 or preferably 6-membered carbocyclic rings fused on. Examples of reactive substituents on the heterocycle include:

• Halogen (CI, Br or F), ammonium including hydrazinium, sulfonium, sulfonyl, azido (N ₃ ), rhodanido, thio, thiol ether, oxyether, sulfinic acid and sulfonic acid. The following can be mentioned in detail, for example:
  • Mono- or dihalo-symmetrical-triazinyl residues and mono-, di- or trihalopyrimidinyl residues.

Suitable phenolic or enolic coupling components for the process according to the invention are preferably those of the Naphthol-AS series.

Naphtol AS-G:

Naphtol AS-D:

p Chloranilid der 2-Hydroxycarbazol-3-carbonsäure

Naphthol AS-ITR:

Naphthol AS-IRG:

Naphthol AS-OL:

Geeignete Pyrazolone sind z.B. das Natriumsalz des 1-(3-Sulfophenyl)-3-methyl-pyrazolons-(5) oder das Dinatriumsalz der 1-(4-Sulfophenyl)-5-pyrazolon-3-carbonsäure.The following are examples: Naphtol AS:

Naphtol AS-G:

Naphtol AS-D:

p Chloranilide of 2-hydroxycarbazole-3-carboxylic acid

Naphthol AS-ITR:

Naphthol AS-IRG:

Naphthol AS-OL:

Suitable pyrazolones are, for example, the sodium salt of 1- (3-sulfophenyl) -3-methyl-pyrazolone- (5) or the disodium salt of 1- (4-sulfophenyl) -5-pyrazolone-3-carboxylic acid.

Stabilized diazonium salts include, in particular, true color salts, which act as stabilizers Contain zinc chloride, aromatic sulfonic acids or tetrafluoroboric acid. The stabilized diazonium salts were either used as aqueous pastes or converted into aqueous diazonium salt solutions before the coupling reaction.

• Echtbraunsalz V: Azoic Diazo Component 21 (CI-Nr. 37200)
• Echtbordosalz GP: Azoic Diazo Component 1 (CI-Nr. 37135)
• Echtrotsalz TR: Azoic Diazo Component 11 (CI-Nr. 37085)
• Echtrotsalz RC: Azoic Diazo Component 10 (CI-Nr. 37120)
• Echtblausalz BB: Azoic Diazo Component 20 (CI-Nr. 37175)
• Echtschwarzsalz BTL: Azoic Diazo Component 38 (CI-Nr. 37190)

The following stabilized diazonium salts are listed as examples:

• Real brown salt V: Azoic Diazo Component 21 (CI No. 37200)
• Real Bordosalz GP: Azoic Diazo Component 1 (CI No. 37135)
• True red salt TR: Azoic Diazo Component 11 (CI No. 37085)
• Real red salt RC: Azoic Diazo Component 10 (CI No. 37120)
• Real Blue Salt BB: Azoic Diazo Component 20 (CI No. 37175)
• Real black salt BTL: Azoic Diazo Component 38 (CI No. 37190)

In addition to the solvent water, the paste containing the reservation agent and the reactive dye also contains alkali (in particular soda or sodium hydroxide solution) and optionally thickeners (e.g. starch ether thickening).

In addition to the solvent water, the paste containing the stabilized diazonium salt also contains acid (preferably acetic acid), thickeners and optionally other auxiliaries, such as defoamers (e.g. isooctyl alcohol or silicone oils).

The pressure is generally dried at approx. 90-120 ° C, especially at approx. 100 ° C. The excess phenolic or enolic coupling component is removed with alkali, in particular with aqueous alkali hydroxide.

The reactive dye is fixed with alkali by methods known per se.

• Das Reservemittel wird mit einem Reaktivfarbstoff in eine Druckpaste eingearbeitet, mustergemäß auf ein mit (^R) Naphthol AS, AS-G, AS-D oder mit anderen geeigneten Naptholen präpariertes Baumwollgewebe oder - gewirke aufgedruckt, dann naß-in-naß ein stabilisiertes Diazoniumsalz im Überfall übergedruckt und getrocknet.

The following embodiment of the method according to the invention is particularly preferred:

• The reserve medium is worked into a printing paste with a reactive dye, printed onto a cotton fabric or knitted fabric prepared with ( ^R ) Naphthol AS, AS-G, AS-D or with other suitable naphthols, then wet-on-wet a stabilized diazonium salt in Overprint printed and dried.

The reactive dye is then subjected to a one-stage steaming process or a two-phase development, e.g. Alkaline pad damping process or alkali shock process or cold residence process, fixed on the cellulose material and then the textile thus printed and treated is subjected to a washing process to remove the excess naphthol. You get attractive, patterned real prints.

Some embodiments of the method according to the invention are described below by way of example.

example 1

A cotton fabric primed with a solution of 10-20 g Napthol AS is printed with a printing paste of the following composition on the rotary film printing machine in small-area patterns, for example dots or sheet contours:

1000 g printing paste

Instead of 30 g of soda (calc.), 30 g of sodium hydroxide solution (38 ° Be) can be used in the production of the printing paste.

A larger area is overprinted wet-on-wet over the pre-printed reserve ink with a second stencil. This printing paste has the following composition:

The dried pressure is steamed for 6 minutes at 100-102 ° C in the continuous steamer, then in cold Rinsed water and aftertreated in another bath containing 1-5 g of soda or 1-5 g of sodium hydroxide solution at 38 ° Be / 1 to remove the excess naphthol at 90-100 ° C. A second alkaline aftertreatment of this kind can have an advantageous effect on the cleanliness of the fund. It is then rinsed cold and dried. Gold-yellow reserve prints are obtained under a brown surface.

Example 2

Printing on a printing paste with reserve means, as described in Example 1. In the wet-on-wet attack, a printing paste of the following composition is overprinted:

After drying, the goods are passed through an alkaline bath of the following composition in the broad state:

Fleet temperature: 85-95 ° C, diving time 8-12 seconds

The printed goods are then washed out and dried in a manner analogous to that described in Example 1. You get golden yellow reserve effects under bordo-colored overprint.

Example 3

A 3-color sample is printed on the rotary film printing machine on Naphthol AS primed cotton fabric.

On these two pre-printed colors, wet-on-wet is printed with a third stencil in the attack with the following composition:

3. Stencil: printing paste off

After drying, the goods are padded on a padder with an alkaline liquor of the following composition:

Fleet temperature: room temperature and steamed in a suitable quick steamer at a steam temperature of 110-160 ° C for 6 - 35 seconds.

Then, as described in Example 1, washed and dried.

You get white and yellow reserve effects under a red area.

Example 4

On a rotary film printing machine, a cotton fabric primed with Naphthol AS-G is printed with a printing paste of the following composition:

Nach dem Trocknen wird die bedruckte Ware auf dem Foulard mit einer Flotte folgender Zusammensetzung:

A printing paste of the following composition is overprinted wet-on-wet with another stencil:

After drying, the printed goods are placed on the padder with a fleet of the following composition:

impregnated at room temperature, docked and lingered at room temperature for about 4 hours. Then it is washed and dried as described in Example 1.

You get red reserve effects under a yellow area.

Printing pastes 1. 60 a reserve means (as in Example 1) are placed in succession on a Rouleaux printing machine on Naphthol AS-primed goods.

After drying, the printed goods are steamed for 6 minutes at 102 ° C. in a hanging loop damper and then subjected to the aftertreatment described in Example 1.

Yellow, red and blue reserve effects are obtained under a bordo-colored area.

Example 6

wird mit Hilfe einer Rotationsschablone in Form von Punkten auf mit Naphthol AS präparierte Ware aufgedruckt. Darauf wird naß-in-naß im Überfall ein 2-farbiges Flächenmuster übergedruckt.

is printed on a product prepared with Naphthol AS using a rotary stencil in the form of dots. A two-colored surface pattern is overprinted wet-on-wet in the holdup.

Printing paste 1st surface:

Nach dem Trocknen wird die Ware 3-6 Minuten bei 102°C gedämpft und, wie in Beispiel 1 aufgeführt, einer Nachwäsche unterzogen.

After drying, the goods are steamed for 3-6 minutes at 102 ° C and, as listed in Example 1, subjected to a post-wash.

You get light blue reserve effects under a black or dark blue area.

Claims (5)

1. Process for producing resist prints on fibre materials consisting of cellulose or containing cellulose, which materials are printed or grounded with a phenolic or enolic coupling component, by printing on to said materials a resist which prevents the formation of a water-insoluble azo dyestuff, subsequently over-printing with a stabilising diazonium salt, washing out the soluble constituents and finishing the print in a customary manner, characterised in that the resist contains a pyrazolone derivative as the resist agent.

2. Process according to Claim 1, characterised in that the resist agent is 1-(3-sulphophenyl)-3-methylpyrazol-5-one.

3. Process according to Claim 1, characterised in that the resist agent is 1-(4-sulphophenyl)-3-carboxypyrazol-5-one.

4. Process according to Claim 1, characterised in that the resist additionally contains one or more reactive dyestuffs.

5. Process according to Claim 1, characterised in that the fibre materials printed with the coupling component are overprinted with overlapping, by the wet-on-wet method.