DE2842473A1 - Transfer printing cellulosic fabrics - impregnated with crosslinkable (phenyl)-triazine derivs. - Google Patents

Abstract

In a process for transfer printing cellulose-contg. textiles the fabric is first impregnated with an aq. or aq./alcoholic soln. of cross-linkable triazine derivs. (I) and/or (II). The fabric is then dried and transfer printed with sublimable dyes. The triazine cpds. (I) and/or (II) are cross-linked by the action of heat before or during the transfer printing stage. The triazine cpds. (I) and have formula (II). In (I), 0-2 R gps. are H; 2-5 R gps. are R1-OCH2- gps. in which R1 is H or 1-4C alkyl; 1-3 of R gps. are R2-O-CH2- gps. in which R2 is a gp. R3-O-(CH2-CR4HO)n in which R3 is 1-7C alkyl or 8-22C alkyl or alkylaryl gp., R4 is H and/or CH3 and n is 5-30; and 0-2 R gps. are R5-O-CH2 gps. and/or R5-COOCH2- gps. in which R5 is 8-22C alkyl- or alkylaryl gps.; with the proviso that 0.1-2 gps. R are R5-O-CH2 gps. if R3 is 1-7C alkyl. (II) are of the same formula except that one NR2 gp. is replaced by phenyl. In (II), none of the R gps. are H; 2.1-3.9 of the R gps. are R1-O-CH2; 0.1-1 of the R gps. are R2-O-CH2- gps.; and 0-0.9 of the R gps. are R5-O-CH2 and/or R5-COOCH2 gps. where R1-5 are as for (I). The treatment with the triazine cpds. improves the affinity of the textiles.

Description

"Process for printing cellulose textiles"

Addition to patent .. .. ... (patent application P 28 37 385.5 (D 5776)) Subject of the main patent .. .. ... (patent application P 28 37 385.5 (D 5775)) is a process for printing cellulose fibers containing textile materials after the transfer printing process with the aim of transfer printing onto cellulose textiles in terms of dye yield, color brilliance, rubbing fastness, washability and handle to further improve the printed textile material.

The process is characterized in that the fabric is treated with an aqueous or aqueous-alcoholic solution of crosslinkable triazine derivatives of the general formula with the following meaning for the substituents R: a) O-2 of the substituents are hydrogen b) 2-5 of the substituents are Rl-O-CH2 radicals; R¹ = hydrogen or alkyl with 1-4 carbon atoms c) 1-3 of the substituents are R2-0-CH2 radicals; R2 = R3-O (-CH2-CHO) n; R4 R3: alkyl with 1-7 or alkyl or alkylaryl with 8-220 atoms; R = hydrogen and / or methyl; n = 5 - 30 d) O - 2 of the substituents are R5-0-CH2 and / or R5-COOCH2 radicals, R5 = alkyl or alkylaryl with 8-22 0 atoms, with the proviso that d) 0, 1-2 is, if R3 = alkyl with 1-7 carbon atoms, impregnated in the presence of a catalyst causing the crosslinking, dried and then the transfer printing process is carried out with sublimable dyes, the crosslinking taking place before or during the transfer printing by the action of heat .

In a further development of the process of the main patent, it has now been found that with equal or better success the triazine derivatives of the main patent can completely or partially replace by certain diaminophenyltriazine derivatives.

The invention thus provides a method for printing cellulose fiber-containing textile materials by the transfer printing method according to the main patent ..,. ... (Patent application P 28 37 385.5 (D 5776)), characterized in that the fabric with an aqueous or aqueous-alcoholic solution of crosslinkable diaminophenyltriazine derivatives of the general formula with the meaning given in claim 1 for R impregnated in the presence of a catalyst causing the crosslinking, dried and then carried out the transfer printing process with sublimable dyes, the crosslinking taking place before or during the transfer printing by the action of heat. It is also possible to use mixtures of a diaminophenyltriazine compound and a triazine compound according to the main patent, the mixing ratio preferably being 80:20 to 20:80 percent by weight.

Textiles made from natural or regenerated materials are used for the process Cellulose and mixed textiles with a proportion of synthetic fibers, e.g. B. polyamide or polyester fibers. The pretreatment according to the invention is carried out by Impregnation of textiles with an aqueous or aqueous-alcoholic solution of the claimed diamino-phenyltriazine derivatives in the usual way by exchanging, spraying, Padding or the like.

The solutions contain 35 to 100 g / l of triazine compound in addition to 3.5 up to 10 g / l of a conventional acidic or acid-releasing curing catalyst, e.g. B; ZnCl2, MgCl2, Al2 (S0) 3. After impregnation, the textile material should be 1 - 5 Contain% by weight of diamino-phenyltriazine derivative.

The liquor can also contain conventional softeners, water repellants, Wetting agents, for example non-ionic ethylene oxide adducts with higher fatty alcohols or alkylphenols, or the like. Contain. The diamino-phenyltriazine derivatives used however, already have a pronounced finishing effect on their own, so that the use of other softeners is generally not necessary. It is also advisable to use common anti-crease finishing agents at the same time, for example melamine or urea-formaldehyde precondensates, in amounts up to to 50 wt .-% of the diamino-phenyltriazine compound.

After impregnation, the textile material is dried, whereupon the The diamino-phenyltriazine compound can be crosslinked by the action of heat. In this case, temperatures of 140 to 1600 ° C. are used for a period of time applied from 3 to 5 minutes. Appropriately, however, the networking takes place at the same time with the transfer printing, with the temperatures and exposure times used (180 - 210 ° C, 25 to 60 seconds) are generally sufficient.

The diamino-phenyltriazine compounds not only crosslink with one another, but due to their content of reactive methylol groups also with the Cellulose as well as with reactive amino and hydroxy groups of the dyes, thereby an excellent fixation of the dye to the cellulose fiber is achieved, which leads to good dye yield, brilliance and rub fastness, In addition the feel and softness of the textiles as well as the hydrophilicity and washability improved in a surprising way. The equipment with the diamino-phenyltriazine compounds does not produce any signs of yellowing or unpleasant smells or fumes.

The diamino-phenyltriazine compounds are produced in an known manner, one of a polyalkoxymethyl-diaminophenyltriazine with preferably 4 alkoxymethyl groups, in particular methoxymethyl groups, starts out. This is done simultaneously or one after the other with the desired amount of alcohols, Alkylphenols, their alkylene oxide adducts, e.g. ethylene oxide and / or propylene oxide adducts, or carboxylic acids are reacted according to c) or d) of the general formula. the Reaction takes place in the presence of acidic catalysts, preferably paratoluene sulfonic acid, at temperatures of 110-15,000, if necessary under vacuum, until the alkanol is split off is essentially complete, which is checked, for example, by IR spectroscopy no catalysts are required for the reaction with carboxylic acids, the conversion takes place here at 180 - 2000C under vacuum. in performing this Measures are formed in a subordinate amount of precondensates.

Such diamino-phenyltriazine compounds are preferably those specified general formula is used, the substituents R of which have the following meaning: a) none of the substituents is hydrogen, b) 3 of the substituents are R1-0-CH2 radicals; -R1 corresponds to the general formula of claim 1, c) 0.5-1 of the substituents are R2-0-0H2 radicals, R2 = corresponds to the general formula of claim 1 R3 = Alkyl with 1 - 7 carbon atoms R = hydrogen n = 10 - 15, d) O - 0.5 of the substituents R5-0-CH2 radicals and / or R -COOCH2 radicals R5 = straight or branched chain, saturated or unsaturated alkyl with 8-22 carbon atoms.

Soluble, crosslinkable precondensates are also claimed Diamino-phenyltriazine compounds described, as well as corresponding mixed precondensates from the diaminophenyltriazine compounds and the triazine derivatives of the main patent.

Examples Examples of the preparation of diaminophenyltriazine compounds I./1 365.0 g of tetramethoxymethylbenzoguanamine, 500 g of methanol. 10.5 E0 and 2.3 g Paratoluenesulfonic acid are stirred at 130 ° C. until 32.0 g of methanol are split off and the methoxypolyoxyethylene alcohol is quantitatively transetherified. Then the Catalyst neutralized. This gives 833 g of a viscous, water-miscible Liquid.

1.12 1 mol of polymethoxymethylbenzoguanamine is mixed with 0.5 mol of methylglycol . 8 EO and 0.2 mol of dodecanol in the presence of paratoluenesulfonic acid at 13,000.

The resulting product forms a stable dispersion with water.

1.13 1 mol of polymethoxymethylbenzoguanamine is mixed with a mixture from 0 ,. Mol of tallow alcohol 14 EO and 0.9 mol of methyl glycol 1 \ 4 EO in the presence of Paratoluenesulfonic acid is transetherified at 1300C and then the catalyst is neutralized. The result is a product which is cloudy in water and dissolves.

1,111 1 mole of polymethoxymethylbenzoguanamine and 1 mole of technical Polymethoxymethylmelamine is mixed with 2 moles of nonylphenol 9.5 EO in the presence of paratoluene sulfonic acid implemented and then neutralized the catalyst. The resulting product is opalescent, water-soluble.

1 mol of polymethoxymethylbenzoguanamine is applied under a vacuum of 30 mbar with 0.3 mol of lauric acid at temperatures of 150 ° C with elimination of methanol for so long implemented until the SZ v is 5. Then 0.7 mol of methyl glycol 7 EO are mixed in and transetherified at 1300C in the presence of paratoluene sulfonic acid. The product is dispersible in water.

II. Examples of the application of the diamino-phenyltriazine compounds in the case of transfer printing of entirely or partially made of cellulose fiber material Textiles In./1 A cotton poplin is made in the usual way with a liquor containing 40 g / l diamino-phenyltriazine derivative I./1, 4 g / l ammonium chloride and 10 g / l one commercially available, polyethylene-containing finishing agent with a liquor pick-up of 75% padded, dried for 4 minutes at 110 ° C and then for 30 seconds at 1900C under a slight vacuum using a commercially available transfer paper printed on a vacuum transfer calender.

The result is a poplin that is deeply colored and sharp in contours Product appearance with good fastness properties has a smooth, supple handle.

In./2 A cotton / polyester knitted fabric (50/50) is used with an equipment fleet, Contains 30 g / l diamino-phenyltriazine derivative I./2, 3 g / l zinc nitrate and 10 g / l a commercially available, silicone-containing finishing agent for a liquor pickup 35% padded and dried at 1800C for 1 minute. Then 30 seconds at 21000 using a commercial transfer paper that Material subjected to thermal transfer printing. A dimensionally stable, color-fast knitted fabric with brilliant color loss and excellent sewability, so that not a single one was sewn on a 3 m seam using industrial sewing machines with high speeds Mesh burst damage is present.

In, / 3 A cotton pile fabric is made with an equipment fleet containing 35 g / l of the diamino-phenyltriazine derivative I./4, 20 g / l of a commercially available urea-formaldehyde precondensate, 20 g / l of a commercially available, silicone-containing water repellent, 2 g / l of one commercial silicone catalyst and 3 g / l zinc nitrate with a liquor pickup of 85% padded and then dried at 1200C for 3 minutes. To The material is transferred to the transfer printing process in the usual mechanical finishing work subjected under vacuum on a vacuum transfer calender. A hydrophobic one is obtained Goods with finely graduated halftones in excellent brilliance and an open Pile.

In./4 A cotton pile fabric is supplied with an equipment fleet containing 80 g / l of the diamino-phenyltriazine derivative I./5, 40 g / l of a commercially available urea-formaldehyde precondensate as a crease-proof finishing agent, 20 g / l of a commercially available, silicone-containing Water repellent, 2 g / l of a commercially available silicone catalyst and 5 g / l ammonium chloride padded with a liquor pick-up of 85%, dried to 20% residual moisture and subjected to the usual mechanical finishing work.

Then the material is transferred to the transfer printing process under vacuum subjected to a vacuum transfer calender. It becomes a silky, shiny pile fabric obtained with bright and deep shades, which is waterdrop resistant and high Has resilience.

In / 5 A linen fabric is made with an equipment fiotte containing 50 g / l I / 3, 5 g / l of a commercially available catalyst and 1 g / l of a commercially available Padded wetting agent, the liquor pick-up being 75%. The material will dried at 11000 and transfer printed as usual. There is a commodity with even, deeply colored coverings, one not compared to the original product changed base and good creasing properties.

When testing the wash and rub fastness according to DIN 54014 or 54021 a five-point comparison scale is used, with 5 being the best and 1 represents the worst value.

II. / 1 Cotton poplin washfastness according to DIN 54014 change of color Test item 3 staining of accompanying fabric polyester 4 - 5 rayon 4 fastness to rubbing according to DIN 54021 dry 4-5 wet II./2 cotton / polyester knitted fabric Fastness to washing according to DIN 54014. Change in color shade of test item 4. Coloring of accompanying fabric Polyester 5 rayon 5 fastness to rubbing according to DIN 54021 dry 4-5 wet 4 II./3 cotton pile fabric Fastness to washing in accordance with DIN 54014 Change in color of test specimen 2 - 3 Coloring of accompanying fabric Polyester 4 - 5 viscose wool 4 rubbing fastness according to DIN 54021 dry 4-5 wet II. / 4 cotton pile fabric Fastness to washing in accordance with DIN 54014 Change in color shade of test item 3 Coloring of accompanying fabric Polyester 4 - 5 rayon 4 - 5 fastness to rubbing according to DIN 54021 dry 4-5 wet 3 II./5 Linen fabric fastness to washing according to DIN 54019 Change in color of test item 3 Color of Accompanying fabric polyester 4 - 5 rayon 4 fastness to rubbing according to DIN 54021 dry 4 wet 3

Claims (7)

"Process for printing cellulose textiles addendum to patent .. .. ... (patent application P 28 37 385.5 (D 5776)) Patent claims: Q1. Process for printing cellulose fiber-containing textile materials by the transfer printing process according to the main patent .. .. ... (Patent application P 28 37 385.5 (D 5776)), characterized in that the fabric with an aqueous or aqueous alcoholic solution of crosslinkable diaminophenyltriazine derivatives of the general formula with the following meaning for the substituents R: a) none of the substituents is hydrogen, b) 2.1-3.9 of the substituents are R1-OCH2 radicals; R = hydrogen or alkyl with 1 -C atoms, c) 0.1-1.0 of the substituents are R2-O-0112 radicals; R2 R3-O - (- CH2-CHO) n; R R3 = alkyl with 1-7 or alkyl or alkylaryl with 8-24 carbon atoms; R4 = hydrogen and / or methyl; n = 5-30; d) O - 0.9 of the substituents are R5-o-CH - and / or R5-COOCH2 radicals, R5 = alkyl or alkylaryl with 8-22 carbon atoms, impregnated in the presence of a catalyst causing the crosslinking, dried and then the transfer printing process is carried out with sublimable dyes, the crosslinking taking place before or during the transfer printing by the action of heat. 2. The method according to claim 1, characterized by the use of diamino-phenyltriazine compounds of the general formula in which the substituents R have the following meaning: a) none of the substituents is hydrogen, b) 3 der Substituents are R1-0-Cii2 radicals; R1 = corresponds to the general formula, c) 0.5 - 1 of the substituents are R²-O-CH2 radicals, R2 = corresponds to the general formula, R3 = alkyl with 1 - 7 carbon atoms, R = hydrogen, n = 10 - 15, d) O - 0.5 of the substituents are -R5-0-GH2 residues and / or R 5-000CH2 residues, R5 = straight or branched chain, saturated or unsaturated alkyl with 8-22 carbon atoms. 3. The method according to claim 1 and 2, characterized in that the Impregnation liquor 35 to 100 g / l of a diaminophenyltriazine compound or one Mixture of a diaminophenyltriazine compound with a triazine compound of the main patent in a mixing ratio of 80:20 to 20:80 percent by weight. 4. The method according to claim 1-3, characterized in that the Impregnation liquor 3.5 to 10 g / l of an acidic or acid-releasing curing catalyst contains. 5. The method according to claim 1-4, characterized in that the Crosslinking of the diamino-phenyltriazine compounds takes place during transfer printing. 6. The method according to claim 1-5, characterized by the use of soluble, crosslinkable precondensation data of the diamino-phenyltriazine compounds or of corresponding mixed precondensates from the diaminophenyltriazine compounds and the triazine compounds of the main patent. 7. The method according to claim 1-6, characterized by the co-use Conventional anti-crease finishing agents in quantities of up to 50% by weight, based on on diaminophenyltriazine compound.