DE3431365A1 - Printing process for textile material - Google Patents

Abstract

A process for the printing of cellulose or of a textile mixture consisting of cellulose and a natural or synthetic polyamide, characterised in that a) the textile material is printed with a printing paste which contains an anionic, basic or cationic dye and a synthetic thickener, b) the dye is fixed by heating, c) the textile material is treated before or after process steps a) and b) with a fixing agent F), which is a water-soluble product which is obtained by reaction of A) a reaction product of a mono- or polyfunctional primary or secondary amine in the form of the free base or in salt form with cyanamide, dicyandiamide, guanidine or biguanidine, the reaction product obtained containing reactive hydrogen atoms bonded to N atoms, with B) an N-methylol compound of urea, melamine, guanamine, triazinone, urone, urethane, carbamate or acid amide in aqueous solution, together with a catalyst C) for the crosslinking of the N-methylol component and D) a heat treatment for the fixing agent F).

Description

Printing process for textile material

The invention relates to a method for printing textile material made of cellulose or cellulose mixed with polyamide.

It is known to print cotton with direct dyes, whereby the dye is fixed on the fiber by heating and soaped at 40-50 "C, to remove unfixed dye and residual thickener from the printing paste; Finally, the print is treated with a cationic fixing agent. the The fastness of the print is improved in this process; but the effect is often only temporarily and the pressure does not withstand repeated washing.

It has now been found that if a fixative F), as it is in the US Patent 4,410,652 is described as an aftertreatment agent after Printing is used and if there is a synthetic thickener in the printing paste is used, an intermediate washout process can be omitted and furthermore a substantial improvement in the fastness properties can be achieved.

In addition, if the fixing agent F) can also be used as a pretreatment agent is used, there is no need for a washout process after the dye has been fixed.

Accordingly, the subject of the invention is a method of printing of cellulose or a textile mixture consisting of cellulose and a natural one or synthetic polyamide, characterized in that a) the textile material printed with a printing paste that has an anionic, basic or cationic Contains dye and a synthetic thickener, b) fixing the dye by heating, c) treating the textile material before or after the process steps a) and b) with a fixing agent F), which is a water-soluble product that one by implementing of A) a reaction product of a mono- or polyfunctional primary or secondary amine in the form of the free base or in Salt form with cyanamide, dicyandiamide, guanidine or biguanidine, the obtained Reaction product has reactive hydrogen atoms bonded to N atoms, with B) an N-methylol compound of urea, melamine, guanamine, triazinon, urone, Urethane, carbamate or acid amide in aqueous solution, together with a catalyst C) obtained for the crosslinking of the N-methylol component and d) a heat treatment for fixative F).

In process step a), the printing paste advantageously contains one Direct, reactive, acid, pigment, sulfur or vat dye, or a developing dye, (the coupling takes place on the substrate).

The printing paste mainly contains a direct dye, in particular a 1: 1 or 1: 2 metal complex dye, a reactive dye, in particular with a mono-, di- or trihalopyrimidyl or a mono- or dihalogenotriazinyl reactive group, or an acid dye having up to four anionic groups, e.g., -S03H groups. The direct dyes are of particular advantage.

The printing paste contains a synthetic thickener, which advantageously a carboxyl group-containing polymerization product in a salt form, for example salts of polyacrylic acid, polymethylacrylic acid or a copolymer from ethylene and maleic anhydride, as for example from the German Auslegeschrift 2557002 are known.

The printing paste advantageously contains a quantity of a thickener from 0.2 to 5% and preferably 0.5 to 2.0% based on the paste, advantageously Printing pastes with a viscosity in the range from 1 to 20 and preferably 3 to 10 Pascal / sec. used.

The printing paste can also contain the usual additives, e.g. urea, Solvents, Carriers, Anti-Foam Agents, etc.

The fixing step b) can be carried out according to methods known per se e.g. with saturated steam at temperatures around 102 "for 5-40 minutes, advantageously, however, at 10 to 20 minutes or with dry heat at 150 to 200.degree for 30 seconds to 5 minutes, advantageously with superheated steam at 150-200 ° C for 1 to 15 minutes, advantageously for 5 to 10 minutes. The usage of however, synthetic thickener allows the fixing time to be about half to reduce these values, e.g. less than 10 minutes at 102 "C with saturated Water vapor, even for deep staining. The process steps are advantageous c) and d) carried out according to process steps a) and b), i.e. the fixing aid F) is used as an aftertreatment agent. It is not necessary with this procedure the substrate between the fixing step b) and the post-treatment step c) to wash. This means a remarkable advantage compared to known printing processes, which require a time-consuming washout process. In addition, the use results a synthetic thickener leaves less residue on the substrate after drying without washing off, in contrast to the usual conventional used Thickeners, such as carob flour, alginates, etc., the handle after in addition, has not suffered from fixation.

The fixing agent F) is advantageously the reaction product of diethylenetriamine with dicyandiamide and the product obtained further reacted with dimethylol-dihydroxyethylene urea in the presence of a catalyst C).

In the preparation of F) diethylenetriamine and dicyandiamide are used advantageously reacted with one another in a molar ratio of 1: 1 and the catalyst a nitrate, sulfate, chloride or dihydrogen orthophosphate of aluminum is advantageous, Magnesium or zinc, especially magnesium chloride.

The fixative can be produced and used according to the information in US Pat. No. 4,410,652, the exhaust process being at room temperature is preferred. Suitable amounts of auxiliary F) are, for example, 30-200 g per liter Dye liquor for a 1/1 standard dye depth with a squeeze effect from 70-100% based on the dry weight of the substrate, advantageously 70-130 g / l for cotton and 100-200 g / l for regenerated cellulose.

The heat treatment step d) can also be carried out in accordance with the USA patent 4,410,652, e.g. drying at 70-120 "C and curing at 130-180" C for 30 seconds to 8 minutes or with simultaneous drying and crosslinking at 120-200 ° C., advantageously 140-180 ° C. for 5 seconds to 8 minutes, and in particular at 170-180 * C for 30 seconds to 1 minute.

A selection of suitable direct and reactive dyes is also available in U.S. Patent 4,410,652.

The fixing agent F) can also be used as a pretreatment agent be, either by putting the inventive method steps in the order c), d), a), b) carried out by mixing the uncolored substrate with the fixative treated, the treated substrate dries and heat-treated, then printed and finally the dye fixed, or by the inventive Process steps are carried out in the order c), a), b), d).

In this second variant, the fixative F) is applied to the uncolored Brought substrate, which is then optionally printed after an intermediate drying will. Finally, the dye is fixed with the help of a heat treatment and the fixative is crosslinked with heat.

This process can be carried out in two separate steps e.g. by steaming at 102 "C followed by a heat treatment at 1800C or in a single step, e.g. with a dry heat treatment at 150-200 ° C.

Both in process steps c), a), b), d) and c), d), a), b) is not a final washing operation after the final fixing stage necessary. The printed substrate has a good grip and prints are made with it good fastness properties, such as fastness to washing and perspiration, behave.

If the fixative F) is used as an aftertreatment agent surprisingly, without intervening a washing operation, i.e. that an unwashed print when passing through the dyeing tub no longer enters the watery one Fluid is bleeding or that unwashed pressure when passing through the staining trough, which is equipped with an aftertreatment agent, not during padding more bleeds into the aqueous liquid, in addition, the padding rollers are not stained more, i.e. there is no dirty residue on the padding rollers more.

In the following examples the parts mean parts by weight which Percentages by weight and the temperatures are given in degrees Celsius.

Example 1 Step a) A cotton satin fabric is coated with a printing paste printed according to known methods, which is composed as follows: 20 parts of the dye CI Direct Yellow 98, 300 parts of water, 100 parts of urea, 550 parts a synthetic thickener ES% solution of a commercial product the basis of a polyacrylic acid or its sodium or ammonium salt (DAS 25 57 002)]; 30 parts of a solubilizer mixture, consisting essentially of a polyethylene glycol (molecular weight about 300), benzyl alcohol, hexylene glycol, kol, monoethanolamine and water.

1000 parts total Step b) The fixation is done with saturated steam 102 "C for 10 minutes.

Step c) After fixing the unwashed print with a Auxiliaries dissolved in water, 100 g / l, impregnated on the padder and on a Liquor pick-up of about 60% squeezed off, with the product of des as an aid Example 1 of U.S. Patent 4,410,652 is used.

Step d) The treated fabric is placed on the tenter at 80 " dried and then for 30 seconds to 1 minute at 1800 with hot air treated.

The yellow print has good wet fastness properties, e.g. good washing and alkaline fastness to perspiration.

The yellow print does not bleed into the padding liquor during padding off (step c).

Example 2 Step a) A fabric made of 80% cellulose and 20% polyamide, Nylon 6, is printed with a printing paste according to known methods, which like is composed as follows: 10 parts of the dye CI Direct Blue 77, 310 parts Water, 100 parts of urea, 30 parts of solubilizer as in Example 1, 550 parts synthetic thickener as in Example 1, 1000 parts in total.

Step b) The fixation takes place for 90 seconds with hot air 180 ', step c), d) The print is treated according to the information in Example 1, without an intermediate wash, A deep blue coloration with improved color is obtained Wet fastness properties.

Example 3 Example 2 is repeated, but regenerated as a substrate Cellulose used. on gets similarly good results.

Example 4 Flat-film printing is carried out on mercerized cellulose satin fabric a four-color pattern printed with four printing pastes, which are composed as follows are: 1) 20 parts of the dye CI Direct Yellow 98, 2) 10 parts of the dye CI Direct Blue 77, 3) 15 parts of a mixture of 1) + 2) in a ratio of 1: 1 as olive green, 4) 120 parts of a dye based on a stabilized fast dye salt and a naphtholate (known under the name Sinagenrot R from Rhoner).

Pastes 1), 2) and 3) contain 550 parts of a thickener according to Example 1, 30 parts of a water-soluble solubilizer according to Example 1 and water up to 1000 parts in total. Paste 4) contains 600 parts of a thickener according to Example 1, 10 parts of a neutral chromate solution, 30 parts of a water-soluble one Solubilizer as in Example 1 and water up to 1000 parts in total.

During the fixation, the diazonium salt used couples with the naphthol and forms a chromium complex azo dye.

The fixation and post-treatment of the unwashed print is carried out according to example 1. A print is obtained with good fastness properties, such as water, Wet ironing, washing, perspiration and rubbing fastness.

Example 5 Step c) A mercerized cotton fabric is 120 g / l of the auxiliary from Example 1 of US Pat. No. 4,410,652 for a liquor pickup 80% impregnated and dried.

Step d) The dried fabric is placed on a tenter frame during Condensed for 30 seconds at 1800C.

Step a) A two-color print is made on the fabric treated in this way carried out using two printing pastes according to Example 1 containing 1) 20 parts CI Direct Yellow 162 2) 10 parts CI Direct Blue 77.

Step b) After drying, the print is at 102 "C for 10 minutes muffled.

The print shows good wet fastness properties, even without a washout operation the fixation of the dye.

Example 6 Example 5 is repeated without following the step c) the dried but untreated substrate is printed a); the pressure is through Steaming at 102 'is fixed for 10 minutes (step b) and at the end the pressure is 30 Treated for seconds at 1800C (step c). The results will be similarly good obtain.

Examples 7 to 12 Example 1 is repeated with the dyes; CI Direct Red 83 CI Direct Violet 66 CI Direct Blue 251 CI Direct Black 118 CI Dirct Green 69 CI Direct Brown 240.

Similar good results are obtained.

Claims (10)

Claims / 1 method for printing cellulose or from a textile mixture consisting of cellulose and a natural or synthetic one Polyamide, characterized in that a) the textile material with a printing paste printed with an anionic, basic or cationic dye and a synthetic one Contains thickening agent, b) fixing the dye by heating, c) treating of the textile material before or after process steps a) and b) with a fixing agent F), which is a water soluble product obtained by reacting A) a Reaction product of a mono- or polyfunctional primary or secondary amine in the form of the free base or in salt form with cyanamide, dicyandiamide, guanidine or Biguanidine, the resulting reaction product being hydrogen atom reactive at N atoms has bound, with B) an N-methylol compound of urea, melamine, guanamine, Triazinon, urone, urethane, carbamate or acid amide in aqueous solution together with a catalyst C) for the crosslinking of the N-methylol component and d) a heat treatment for the fixing agent F). 2. The method according to claim 1, characterized in that the steps c) and d) are carried out according to steps a) and b), 3. Procedure according to Claim 1, characterized in that between steps b) and c) not is washed out. 4. The method according to claim 1, characterized in that the steps in the order c), d), a), b). 5. The method according to claim 1, characterized in that the steps in the order c), a), b), d). 6. The method according to claim 1, characterized in that the printing paste a direct dye, a reactive dye or an acid dye with up to contains to 4 acidic groups. 7. The method according to claim 1, characterized in that the printing paste contains a 1: 1 or 1: 2 metal complex dye. 8. The method according to claim 1, characterized in that one as Thickener Polymers uses their carboxylic acid groups in the form of salts are present. 9. The method according to claim 1, characterized in that the fixing agent F) is a reaction product of diethylenetriamine with dicyandiamide, which product with dimethylol dihydroxyethylene urea in the presence of a catalyst C) is implemented. 10. The method according to claim 1, characterized in that the Fixing agent F) a reaction product of diethylenetriamine with dicyandiamide in one Molar ratio of 1: 1 is which product with dimethylol-dihydroxyethylene urea is reacted in the presence of magnesium chloride.