GB2031029A

GB2031029A - Transfer Printing of Cellulose Fibres

Info

Publication number: GB2031029A
Application number: GB7929571A
Authority: GB
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1978-08-26
Filing date: 1979-08-24
Publication date: 1980-04-16
Also published as: IT1123542B; GB2031029B; IT7925192A0; TR20316A; NL7906009A; ES483614A1; FR2434231A1

Abstract

In transfer printing textile material containing cellulose fibres the fabric is impregnated with an aqueous or aqueous alcoholic solution of cross- linkable triazine derivatives of formulae <IMAGE> in which the R's are a) 0 to 2 are hydrogen, b) 2 to 5 are R<1>-OCH2 groups, in which R<1> represents hydrogen or alkyl with 1-4 carbon atoms, c) 1 to 3 are R<2>-O-CH2 groups, in which R<2> represents <IMAGE> R<3> represents alkyl with 1 to 7 or alkyl or alkylaryl with 8 to 22 carbon atoms, R<4> represents hydrogen and/or methyl, and n=5-30, d) 0 to 2 are R<5>-O-CH2 and/or R<5>-COOCH2 groups, in which R<5> represents alkyl or alkylaryl with 8 to 22 carbon atoms, provided that d) is 0.1 to 2 when R<3> represents alkyl with 1 to 7 carbon atoms, and/or <IMAGE> in which the R's are a) none is hydrogen, b) 2.1 to 3.9 are R<1>-OCH2 groups, in which R<1> is as above c) 0.1 to 1.0 are R<2>-O-CH2 groups, in which R<2> is as above; R<3> represents alkyl with 1 to 7 carbon atoms or alkyl or alkylaryl with 8 to 24 carbon atoms, R<4> is as above d) 0 to 0.9 are R<5>-O-CH2 groups, in which R<5> represents alkyl or alkylaryl having 8 to 22 carbon atoms, in the presence of a cross-linking, catalyst, and the materials are dried, printing is then carried out using sublimable dyes cross-linking taking place before or during printing by the action of heat.

Description

SPECIFICATION Method of Printing Cellulose Textiles This invention relates to a method of printing cellulose textiles by the heat-transfer printing process with the object of improving the tinctorial power and brilliance of such prints and their fastness to rubbing.

The heat-transfer printing process is becoming increasingly important in the finishing of textiles because it provides a relatively simple means of printing textiles. Moreover, the process is environmentally advantageous since it requires no aqueous or solvent-containing dyeing or aftertreatment liquors.

In this process, dyes which are capable of sublimating, preferably disperse dyes, are printed on transfer paper from which they are transferred to the textile by heat and pressure, using transfer printing machines. A detailed description of the process may be found in "Textilbetrieb" April 1 974, pages 50-53.

The heat-transfer printing process could so far only be carried out without problems on synthetic fibre materials, particularly polyester materials. The printing of cellulose textiles by this process involves problems because the dyes available for the transfer printing process have insufficient affinity for cellulose fibres, and disadvantages such as low dye yield and insufficient brilliance and fastness to rubbing and washing are unavoidable.

It has already been proposed that cellulose textiles which are to be printed by transfer printing should first be treated with auxiliary agents which act both as solvents for the transfer dyes and as potential cross-linking agents for the cellulose. Transfer printing is then carried out in the presence of a cross-linking catalyst when the textile has been dried. The auxiliary agents used may be bi-functional or poly-functionai methylolated and etherified urea derivatives or melamine derivatives or they may be carbamates which may contain a polyglycoi ether group having from 1 to 20 ethylene oxide units.

Metal or ammonium salts of volatile acids applied to a special auxiliary carrier are required as catalysts for the cross-linking reaction. The consequent cost in material and financial outlay is considerable (German Auslegeschrift No. 2,502,590).

It is an object of the present invention to provide further improvement in the transfer printing of cellulose textiles with regard to dye yield, colour brilliance, fastness to rubbing and washing and handle. The invention therefore relates to a process for the printing of textile materials containing cellulose fibres by the transfer printing process, in which the textile materials are impregnated with an aqueous or aqueous alcoholic solution of a cross-linkable triazine derivative corresponding to the following general formula:

in which the substituents R have the following meaning:: a) O to 2 of the substituents are hydrogen; b) 2 to 5 of the substituents are R1--OO-CH, groups in which R2 represents

R3 represents alkyl with 1 to 7 carbon atoms or alkyl or alkylaryl with 8 to 22 carbon atoms, R4 represents hydrogen and/or methyl, and n=5 to 30, d) O to 2 of the substituents are RS--OO-CH, and/or R5COOCH2 groups, in which R5 represents alkyl or alkylaryl having 8 to 22 C atoms, under the condition that the number of substituents d) is 0.1 to 2 when R3 represents an alkyl group with 1 to 7 carbon atoms, and/or the following general formula:

in which the substituents R have the following meaning:: a) none of the substituents is hydrogen, b) 2.1 to 3.9 of the substituents are R1--OCH, groups, in which P1 represents hydrogen or alkyl with 1 to 4 carbon atoms, c) 0.1 to 1.0 of the substituents are R2--OO-CH, groups, in which R2 represents

R3 represents alkyl with 1 to 7 carbon atoms or alkyl or alkylaryl with 8 to 24 carbon atoms, R4 represents hydrogen and/or methyl, and n=5 to 30, d) O to 0.9 of the substituents are P5-0-CH2 and/or P5-CO0CH2, groups, in which R5 represents alkyl or alkylaryl with 8 to 22 carbon atoms, in the presence of a cross-linking catalyst, and dried, and the transfer printing process is thereafter carried out with dyes which can be sublimated, cross-linking being carried out before or during transfer printing by the action of heat.

The textiles to which the process is applied may be natural or regenerated cellulose fabrics or mixed textiles containing a proportion of synthetic fibres, e.g. polyamide or polyester fibres. The preliminary treatment according to the invention is carried out by impregnating the textiles with an aqueous or aqueous alcoholic solution of the triazine derivative according to the invention by any of the usual methods such as immersion, spraying, or slop padding or the like. The solutions contain from 35 to 100 g/l of triazine compound in addition to from 3.5 to 10 g/l of one of the usual acid or acidreleasing hardening catalysts such as, for example, ZnCI2, MgCI2 or Al2(SO4)3. The textile materials should contain from 1 to 5% by weight of triazine derivative after impregnation.

The liquor may also contain the usual brightening agents or wetting agents such as, for example, non-ionogenic ethylene oxide adducts of higher fatty alcohols or alkylphenols, although the triazine derivatives used have a pronounced brightening action on their own so that the use of additional brightening agents is generally unnecessary. It is also advantageous to add the usual crease resisting agents such as, for example, melamine-formaldehyde or ureaformaldehyde precondensates, in quantities of up to 50% by weight of the triazine compound.

After impregnation, the textile material is dried, whereupon cross-linking of the triazine compound by heat may be carried out. Temperatures from 140 to 1 600C are used for 3 to 5 minutes for this reaction. If, however, cross-linking is carried out simultaneously with transfer printing the temperatures and times employed for this process (180 to 2100C, 25 to 60 seconds) are generally sufficient.

The triazine compounds not only cross-link with each other but, due to the reactive methylol groups contained in them, they also cross-link with the cellulose and with reactive amino and hydroxyl groups of the dyes. The dye is thereby very firmly fixed to the cellulose fibres, with the result that a high tinctorial power for a given quantity of dye and great brilliance and fastness to rubbing are obtained. In addition, a surprising improvement is obtained in the handle and flexibility of the textiles and their hydrophilic character and washing characteristics. The finishing treatment with the triazine compounds does not produce any phenomena of yellowing or unpleasant odours or vapours.

The triazine compounds are prepared by known methods from a polyalkoxy methyl melamine preferably having five or six alkoxy methyl groups or from a polyalkoxy methyl-diaminophenyl triazine preferably having four alkoxymethyl groups, in particular methoxymethyl groups. This starting material is reacted simultaneously or successively with the desired quantity of alcohols, alkyl phenols, their alkylene oxide adducts, e.g. their ethylene oxide and/or propylene oxide adducts, or carboxylic acids corresponding to c) or d) of the general formula. The reaction is carried out in the presence of acid catalysts, preferably paratoluene sulphonic acid, at temperatures from 110 to 1 500 C, optionally under vacuum, until the release of alkanol has been substantially completed; this can be checked, for example, by IR spectroscopy. The reaction with carboxylic acids requires no catalysts and is carried out under vacuum at 180 to 2000C. When these methods are adopted, minor quantities of precondensates are formed. For further information on the reaction conditions, see Helvetica Chimica Acta 24(1941) pages 302 etseq.

It is preferable to use those triazine compounds of the general formula indicated above in which the substituents R have the following meaning: For Formula (I): a) O to 2 of the substituents are hydrogen, b) 3 to 4 of the substituents are P1-O-CH2 groups, in which R' is defined for the general formula, c) 1 to 2 of the substituents are R2--OO-CH, groups, in which R2 is defined for the general formula, R3 represents alkyl with 1 to 7 carbon atoms, R4 represents hydrogen and n=1 0 to 15, d) 0.1 to 1 of the substituents are P5-O-CH2 groups and/or R5COOCH2 groups, in which R5 represents a straight chain or branched chain saturated or unsaturated alkyl group with 8 to 22 carbon atoms; For Formula (ill):: a) none of the substituents is hydrogen, b) 3 of the substituents are R1-0-CH2 groups, in which R1 is defined for the general formula c) 0.5 to 1 of the substituents are R2-0-CH2 groups, in which R2 is as defined for the general formula R3 represents alkyl with 1 to 7 carbon atoms, R4 represents hydrogen and n=1 0 to 15, d) O to 0.5 of the substituents are R6-O-CH2 groups and/or R5COOCH2 groups in which R5 represents a straight chain or branched chain saturated or unsaturated alkyl group with 8 to 22 carbon atoms.

Soluble, cross-linkable precondensates of the above described triazine-compounds and mixed precondensates of the triazine compounds of formulae (I) and (II) are also claimed.

1. Examples of the Preparation and Use of Triazine Compounds of Formula (I) 1/1. 390 g of polymethoxy methyl melamine are transetherified with 500 g of methyl glycol. 9.6 EO and 20 g of fatty alcohol C,OC,8 in the presence of paratoluene sulphonic acid at 1300 C. The catalyst is then neutralized. About 865 g of a viscose product which is miscible with water in any proportions are obtained.

1/2. 1 mol of polymethoxy methyl melamine is transetherified with 1 mol of nonyl phenyl. 9.5 EO in the presence of paratoluene sulphonic acid at 1 350C. The resulting product forms a stable dispersion with water.

1/3. 1 mol of polymethoxy methyl melamine is transetherified with 2 mol of ethyl glycol. 5 PO/5 EO and 0.5 mol of a tallow alcohol mixture (C16-C16) in the presence of paratoluene sulphonic acid. The product obtained has a pasty-viscous consistency and is soluble in hot water.

1/4. 1 mol of polymethoxy methyl melamine is transetherified with 1 mol of methyl glycol. 9.6 EO and 1 mol of fatty alcohol (carbon chain distribution: 10% C,O,50% Cur2,20% Cur4,10% C16 and 10% C,8) in the presence of paratoluene sulphonic acid at 1 300C. A pale yellow liquid which is soluble in water to form an opalescent solution is obtained.

1/5. 1 mol of polymethoxy methyl melamine is reacted with 1 mol of hydro-tallow fatty acid (C,,--C,,) at temperatures of up to 1 80/2000C under a vacuum until the acid number is 5. The resulting fatty acyloxy methyl polymethoxy methyl melamine derivative is subsequently etherified with 1 mol of methyl glycol. 1 5 EO to form a product which is dispersible in water 1/6. 1 mol of polymethoxy methyl melamine is reacted as described above with 1 mol of commercial oleyl alcohol and 1 mol of methyl alcohol. 12 EO. A pale yellow substance which dissolves in water to form an opalescent solution is obtained.

1/7. 1 mol of polymethoxy methyl melamine is transetherified with 1 mol of octadecanol. 8 EO in the presence of paratoluene sulphonic acid. A mass is dispersible in water is obtained.

1/8. A cotton fabric is dyed by padding in the usual manner, using a liquor containing 35 gIl of triazine derivative 1/1 to 3.5 g/l of a commercial catalyst, the fabric absorbing 75% of liquor. The fabric is then dried for 5 minutes at 11 00C before it is printed by the heat-transfer printing process, at 21 00C for 30 seconds, using the usual commercial transfer paper. The auxiliary agent undergoes crosslinking during this treatment. The printed material has a full, soft handle combined with a colour print of excellent brilliance and good fastness (to washing and rubbing) and improved creasing angles.

1/9. A mixed fabric of polyester and cotton (50/50) is pad dyed with liquor containing 50 g/l of triazine derivative l/1 and 7 g/l of MgCIi6H20, the liquor absorption being 52%. The fabric is then dried for 3 minutes at 1 1 OOC before it is printed for 30 seconds at 21 00C. The print obtained in this case is also distinguished by its depth of colour combined with good fastness properties and improved creasing angles.

1/10. A cotton material and a polyester-cotton material are treated in the same manner with triazine derivative 1/4. A brilliant print is obtained. Compared with the results obtained in Example 1/8, the fastness to rubbing in the dry state is improved.

1/11. A polyester-cotton material (50/50) is treated as in Example 1/9 with a liquor which in addition to triazine derivative 1/1 and a catalyst contains 10 g/l of a commerical non-ionogenic brightening agent (20% of active substance). A soft handle and brilliant print are obtained.

1/12. A shirt fabric of pure cotton is pad dyed in the usual way, using a liquor containing 70 gjl of triazine derivative 1/1 and 7.0 g/l of a commercial catalyst, the liquor absorption being 75%. The fabric is then dried for 2 minutes at 11 00C before it is printed by the heat-transfer printing process at 21 00C for 30 seconds, using a commerical transfer paper at a contact pressure of 7 g/cm2. No troubiesome vapours develop even when the installation has been in operation for several hours. The shirt material obtained has a brilliant print with great depth of colour.

1/1 3. A knitted fabric of polyester/cotton (50/50) is pad dyed with a liquor containing 35 g/l of triazine derivative 1/4 and 3.5 g/l of a commercial catalyst, the liquor absorption being 60%, and the fabric is then treated as described in Example 1/12. A dimensionally stable, elastic knitted material having a brilliant print and the following fastness properties is obtained: Wash fastness according to DIN 54 014: Sample used to test colour tone change 4 Discolouration of accompanying fabric Polyester 5 Cotton 5 Fastness to rubbing according to DIN 54 021: Dry 4 Wet 3-4 When testing for fastness to washing, rubbing and perspiration according to DIN, a 5-stage marking scale is used to which 5 is the best result and 1 the poorest result.

1/14. A woven fabric of Polyester/rayon (70:30) is treated in the manner described above with a finishing liquor containing 35 g/l of the auxiliary agent according to 1/4 and 3.5 g/l of magnesium chloride.6H2O and printed by the transfer printing process.A print with deep colour tone and nonyellowing white background is obtained Wash fastness according to DIN 54 014: Sample used to test colour tone change 4 Discolouration of accompanying fabric Polyester 5 Rayon 5 Wash fastness according to DIN 50 010: Sample used to test colour tone change 3-4 Discolouration of accompanying fabric Polyester 5 Rayon 5 Resistance to perspiration according to DIN 54 020: Sample to test alkaline colour, tone change 4 Discolouration of accompanying fabric Polyester 4 Rayon 3-4 Sample used to test acid colour tone change 4 Discolouration of accompanying fabric Polyester 4 Rayon 3-4 Light fastness according to DIN 54 003: 7 For the light fastness test according to DIN, an 8-stage marking scale is used, in which 8 represents the best result and 1 the poorest. The creasing angles are substantially improved.It is surprisingly found that the absorbency of the fabric is not signficantly affected whereas the usual easy-care finishes render the fabric hydrophobic.

II. Examples of the Preparation and Use of Triazine Compounds of Formula (Il) 11/1 365.0 g of tetramethoxy methyl benzoguanamine, 500 g of methanol. 10.5 EO and 2.3 g of paratoluene sulphonic acid are stirred at 1 300C until 32.0 g of methanol has been split off and the methoxy polyoxy ethylene alcohol have been quantitatively transetherified. The catalyst is then neutralised. 833 g of a viscous, water miscible liquid are obtained.

11/2. 1 mol of polymethoxy methyl benzoguanamine is transetherified with 0.5 mol of methyl glycol .8 EO and 0.2 mol of dodecanol in the presence of paratoluene sulphonic acid at 1 300C. The product obtained forms a stable dispersion with water.

11/3. 1 mol of polymethoxy methyl benzoguanamine is transetherified with a mixture of 0.1 mol of tallow alcohol. 14 EO and 0.9 mol of methyl glycol. 4 EO in the presence of paratoluene sulphonic acid at 1300C and the catalyst is then neutralised. A product which forms a cloudysolution in water is obtained.

lav4. 1 mol of polymethoxy methyl benzoguanamine and 1 mol of commercial polymethoxy methyl melamine are reacted with 2 mol of nonylphenol . 9.5 E0 in the presence of paratoluene sulphonic acid, and the catalyst is then neutralised. The resulting product forms an opalescent solution in water.

ill/5. 1 mol of polymethoxy methyl benzoguanamine is reacted with 0.3 of lauric acid under a vacuum at a temperature of 1500C. Methanol is split off and the reaction is continued until the acid number is below 5. 0.7 mol of methyl glycol. 7 E0 are then added and transetherification is carried out at 1300C in the presence of paratoluene sulphonic acid. The product is dispersible in water.

ill/6. A cotton poplin is slop padded in the usual manner, using a liquor containing 40 g/l of triazine derivative 11/1, 4 g/l of ammonium chloride and 10 g/l of a commercial brightening agent containing polyethylene. The absorption of liquor is 75%. The fabric is dried for 4 minutes at 11 OOC and then printed on a vacuum transfer calender roll at 1900C for 30 seconds under a light vacuum, using a commercial transfer paper. The poplin combines depth of colour and sharp contours of the print with good fastness properties and a smooth, flexible handle.

ill/7. A knitted cotton/polyester fabric (50/50) is slop padded with a finishing liquor containing 30 g/l of triazine derivative 11/2, 3 g/l of zinc nitrate and 10 g/l of a commercial brightening agent containing silicone, the liquor absorption being 35%. The fabric is then dried for 1 minute at 1800C and subjected to the heat-transfer printing process for 30 seconds at 2100C, using a commercial transfer paper. A dimensionally stable, colourfast knitted fabric with brilliant colours is obtained. It has excellent properties for sewing so that in a 3 metre seam sewn with a high speed industrial sewing machine, not a single knitted stitch is damaged.

ill/8. A velvet pile cotton fabric is slop padded with a finishing liquor containing 35 g/l of the triazine derivative 11/4, 20 g/i of a commercial urea-formaldehyde precondensate, 20 g/l of a commercial hydrophobisizing agent containing silicone, 2 g/l of a commercial silicone catalyst and 3 g/l of zinc nitrate, the liquor absorption being 85%. The fabric is then dried for 3 minutes at 1200C. After the usual mechanical dressing treatments, the material is transfer printed under a vacuum, using a vacuum transfer calendering roller. A hydrophobic fabric having an open pile and a print of excellent brilliance in finely graded half tones is obtained.

11/9. A velvet pile cotton fabric is slop padded with a finishing liquor containing 80 g/l of the triazine derivative ill/5, 40 g/l of a commercial urea-formaldehyde precondensate as crease resisting agent, 20 g/l of a commercial hydrophobisizing agent containing silicone, 2 g/l of a commercial silicone catalyst and 5 g/l of ammonium chloride, the liquor absorption being 85%. The fabric is dried to a residual moisture content of 20% and subjected to the usual mechanical finishing operations.

The material is then subjected to the transfer printing process under a vacuum, using a vacuum transfer calendering roller. A velvet pile fabric with a silky gloss and luminous, deep colour tones is obtained. The fabric has a high springy elasticity and is resistant to water droplets.

ill/10. A linen fabric is slop padded with a finishing liquor containing 50 g/l of 11/3, 5 g/l of a commercial catalyst and 1 g/l of a commercial wetting agent, the liquor absorption being 75%. The material is dried at 11000 and transfer printed in the usual manner. The fabric obtained has uniform, deeply coloured top shades while the ground shade is unchanged from the original fabric, and the fabric has good crease resistant properties. In the tests for wash fastness and fastness to rubbing according to DIN 54 014 and DIN 54 021, respectively, a 5-stage marking scale is used, in which 5 represents the best value and 1 the worst.

11/6 Cotton Poplin Wash fastness according to DIN 54 041: Sample used to test colour tone change 3 Discolouration of accompanying fabric Polyester 4-5 Rayon 4 Fastness to rubbing according to DIN 54021: Dry 4-5 Wet 3 11/7 Cotton/Polyester Knitted Fabric Wash fastness according to DIN 54 014: Sample used to test colour tone change 4 Discolouration of accompanying fabric Polyester 5 Rayon 5 Fastness to rubbing according to DIN 54 021: Dry 4-5 Wet 4 11/8 Velvet Pile Cotton Fabric Wash fastness according to DIN 54 014: Sample used to test colour tone change 2-3 Discolouration of accompanying fabric Polyester Rayon 4 Fastness to rubbing according to DIN 54021: Dry Wet 3 11/9 Velvet Pile Cotton Fabric Wash fastness according to DIN 54 014: : Sample used to test colour tone change 3 Discolouration of accompanying fabric Polyester Rayon 4-5 Fastness to rubbing according to DIN 54021: Dry Wet 3 11/10 Linen Fabric Wash fastness according to DIN 54 019: Sample used to test colour tone change 3 Discolouration of accompanying fabric Polyester 4-5 Rayon 4 Fastness to rubbing according to DIN 54 021: Dry 4 Wet 3

Claims

1. A process for printing a textile material containing cellulose fibres by the transfer printing process, in which the fabric is impregnated with an aqueous or aqueous alcoholic solution of crosslinkable triazine derivatives corresponding to the following general formula

in which the substituents R have the following meaning:: a) O to 2 of the substituents are hydrogen, b) 2 to 5 of the substituents are R1-0CH2 groups, in which R' represents hydrogen or alkyl with 1-4 carbon atoms, c) 1 to 3 of the substituents are R2--OO-CH, groups, in which R2 represents

R3 represents alkyl with 1 to 7 or alkyl or alkylaryl with 8 to 22 carbon atoms, R4 represents hydrogen and/or methyl, and n=5-30, d) 0 to 2 of the substituents are P6-O-CH2 and/or R5COOCH2 groups, in which R5 represents alkyl or alkylaryl with 8 to 22 carbon atoms, provided that d) is 0.1 to 2 when R3 represents alkyl with 1 to 7 carbon atoms, and/or the following general formula:

in which the substituents R have the following meaning:: a) none of the substituents is hydrogen, b) 2.1 to 3.9 of the substituents are R1-OCH2 groups, in which R1 represents hydrogen or alkyl with 1 to 4 carbon atoms, c) 0.1 to 1.0 of the substituents are P2-0-CH2 groups, in which R2 represents

R3 represents alkyl with 1 to 7 carbon atoms or alkyl or alkylaryl with 8 to 24 carbon atoms, R4 represents hydrogen and/or methyl, and n=5 to 30, d) O to 0.9 of the substituents are R6-0-CH2 groups and/or P6 -COOCH2 groups in which R5 represents alkyl or alkylaryl having 8 to 22 carbon atoms, in the presence of a cross-linking catalyst, and the materials are dried and the transfer printing process is then carried out using dyes which can be sublimated, cross-linking taking place before or during transfer printing by the action of heat.

2. A process as claimed in Claim 1, in which the triazine compound used is a compound of the general formula (I), in which the substituents R have the following meaning: a) 0 to 2 of the substituents are hydrogen, b) 3 to 4 of the substituents are R1-0-CH2 groups, in which R' is as defined in Claim 1, formula 1.

c) 1 to 2 of the substituents are P2H2 groups, in which R2 is defined in Claim 1 formula i.

R3 represents alkyl with 1 to 7 carbon atoms, R4 represents hydrogen, and n=10 to 15, d) 0.1 to 1 of the substituents are R6-0-CH2 groups, and/or R5COOCH2 groups, in which R5 represents a straight or branched chain saturated or unsaturated alkyl group with 8 to 22 carbon atoms.

3. A process as claimed in Claim 1 in which the triazine compound is a compound of the general formula (II), in which the substituents R have the following meaning: a) none of the substituents is hydrogen, b) three of the substituents are R1-0-CH2 groups, in which P1 is as described in Claim 1, formula II, c) 0.5 to 1 of the substituents are R2-0-CH2 groups, in which R2 is as defined in Claim 1, formula 11, R3 represents alkyl with 1 to 7 carbon atoms, R4 represents hydrogen, and n=10 to 15, d) O to 1.5 of the substituents are R5-0-CH2 groups, and/or RS--COOCH, groups, in which R5 represents a straight or branched chain, saturated or unsaturated alkyl group with 8 to 22 carbon atoms.

4. A process as claimed in any of claims 1 to 3 in which the impregnating liquor contains from 35 to 100 g/l of the triazine compound of formula (I) or (II) or a mixture of a triazine compound of formula (I) with a triazine compound of formula (II) in proportions within the range of 80:20 to 20:80% by weight.

5. A process as claimed in any of Claims 1 to 4 in which the impregnating liquor contains from 3.5 to 10 g/l of an acid or acid-releasing hardening catalyst.

6. A process as claimed in any of Claims 1 to 5 in which the cross-linking of the diamino-phenyl triazine compounds takes place during the transfer printing.

7. A process as claimed in any of Claims 1 to 6 in which a soluble, cross-linkable precondensate or corresponding mixed precondensate of triazine compounds of formulae (I) or (II) is used.

8. A process as claimed in any of Claims 1 to 7 in which a crease-resisting agent is added in a quantity of up to 50% by weight, based on the triazine compound.

9. A process as claimed in Claim 1 substantially as herein described with reference to any of the Examples.

10. A textile material which has been printed by a process as claimed in any of Claims 1 to 9.