DE2521595A1 - High mol. wt. polyethylene glycols for textiles dyeing - and simultaneous finishing with practically no colour migration - Google Patents

Abstract

Polyethylene glycols of mol. wt. of 30000-5 x 106, pref. 50000-2 x 106 are used as migration inhibitors for dyeing and simultaneous finishing of textiles, partly contg. cellulose, in a known manner, with water insol. dyestuffs in presence of amino plasts and hardening catalysts. 1-30 pref. 3-20 g/l of polyethylene glycols are used. As aminoplasts the methylol cpds. of urea as well as their mixts. with opt. low alcohol etherified polymethylol melamines are used at 10-100, pref. 15-70 g/l of dry product. Binding agents and other customary finishing means are added, and treatment is in the usual way by padding, drying and condensing. Additionally as aminoplasts, methylol cpds. (opt. low alcohol etherified) of cyclic ureas, carbamates or their mixtures may be used. Furthermore the methylol cpds. of dihydroxy ethylene urea, ethylene urea, propylene urea, hydroxy propylene urea, acetylene diurea and their mixts. with opt. low alcohol etherified polymethylol melamines may be added. The process isused for simultaneous dyeing and finishing of textiles. Practically no migration of dyestuffs occurs and a noticeable increase in dye yield is obtd. Scrubb fastness is improved, crease free effect is not influenced, no impairment of impregnation occurs when water repellent agents are used.

Description

Use of high molecular weight polyethylene glycols in dyeing and simultaneous finishing and method of dyeing and simultaneous finishing of at least partially cellulose-containing textiles The Piimentfärben and simultaneous Finishing of cellulose and cellulose-containing materials is known. Above all also for reasons of rationalization it is becoming more and more important. In addition to the known dyes for pigment coloring and the aminoplast former and the curing catalyst is used in most cases a binder that fixes the dye on the fiber is necessary. However, these binders increase the already existing, disruptive migration, that is, the migration of the dye during drying.

This makes the use of a migration inhibitor in these systems indispensable. The use of alginates and synthetic polymers comes due the influence on the grip of these products is hardly taken into account. According to the state of the art become oxyethylation products when dyeing and finishing together, in particular of alcohols, used for this purpose. The well-known migration inhibitors but have the disadvantage that the migration of the dye is insufficient is prevented. Furthermore, these products have the disadvantage that the dye yield is often unsatisfactory, so lighter colorations result. Also be through these well-known products with a simultaneous hydrophobization the water-repellent Effects adversely affected, It has now been found that using of high molecular weight polyethylene glycols as a migration inhibitor in dyeing and simultaneous finishing of at least partially cellulose-containing textiles with water-insoluble dyes in a known manner according to the prior art occurring disadvantages can be avoided.

The present invention thus relates to the use of polyethylene glycols of molecular weights from 30,000 to 5 million as migration inhibitors Dyeing and simultaneous finishing of at least partially containing cellulose Textiles with water-insoluble dyes in the presence of aminoplasts and curing catalysts in a known way.

In addition, there is a method of dyeing and finishing at the same time of at least partially cellulose-containing textiles with water-insoluble Dyes in the presence of migration inhibitors, aminoplasts, curing catalysts and binders in the usual way by padding, drying and condensing claimed, which is characterized in that the treatment liquors as a migration inhibitor 1 to 30 g / l polyethylene glycols with a molecular weight of 30,000 to 5 million and the Aminoplasts added in amounts of 10 to 100 g / l, calculated as anhydrous product will.

The migration, i.e. unevenness of coloration especially in the area of the Needle bars or clips of the drying units are used for water-soluble dyes is not a practical problem and therefore working with such dyes will be not covered by the subject matter of the present patent application.

According to the invention, polyethylene glycols with a molecular weight of 30,000 are used up to 5 million, in particular 50,000 to 2 million, as migration inhibitors Dyeing with water-insoluble dyes and finishing used at the same time. Polyethylene glycols with a lower molecular weight are not included in the subject matter of the present patent application as this Products do bring about a certain reduction in dye migration, but overall only an effect comparable to the state of the art show, so do not represent an enrichment of the state of the art. As migration inhibitors Polyethylene glycols used are used in the process according to the invention in quantities from 1 to 30 g / l, in particular 3 to 20 g / l, calculated as 100% substances, are used.

For the use according to the invention and the method according to the invention the following water-insoluble dyes are suitable: In the first place The actual pigment dyes come as water-insoluble dyes in question that have no affinity for the fiber and accordingly a binder need, through which the dye is fixed on the fiber. As pigment dyes In addition to the inorganic color pigments, i.e. above all the metal oxides, e.g. the water-insoluble azo dyes, indigoid dyes, diazine, phthalocyanine and metal complex dyes. Also vat dyes in the water-insoluble Shape are suitable.

The chemical constitution of the pigment thus plays a role here not matter.

In addition, the known disperse dyes can also be used. All known disperse dyes are suitable, i.e. all finely divided present water-insoluble color pigments, which from aqueous dispersion on the Fiber are applied and fixed there differently depending on the fiber material will. This is because these dyes behave like cellulosic materials a pigment, so these materials need a binder so a stable color is achieved.

Examples of disperse dyes are those which may be modified Mono- and disazo dyes and antraquinone dyes (also benzane trachinone or Benzanthrone dyes-) called.

A detailed description of the dyes that can be used can e.g. the "Textbook of Textile Chemistry" by H. Rath, Springer Verlag, 3rd edition (1972) can be found under the relevant keyword.

The amount of dye used depends on the depth of color desired away. For light shades, 1 to 3 g / l of commercially available dye are sufficient. Will if, on the other hand, strong colors are required, the dye is used in quantities of up to 50 g / l and more applied.

The water-insoluble dye is common in the process Dyeing and finishing deposited on the surface of the fibers; so it does not occur a binding of the dye to the fiber nor a migration of the dye in the inside of the fiber and it is therefore advisable to use a binder, which fixes the dye on the fiber. The binder that holds the dye particles encloses, forms a firmly adhering film on the fiber and thus holds the dye fixed.

Synthetic copolymers in dispersion form are primarily used as binders are used, which are made from a wide variety of monomers, such as the most diverse Acrylic acid esters, acrylonitrile, vinyl acetate, styrene and optionally polyfunctional ones Monomers, e.g. N-methylolacrylamides, are built up. To ensure a good fixation of the To obtain dye on the fiber, 15 to 100 g / l of the binder are required (based on the present 20 to 50% by weight binder dispersions) used.

Of course, other products can also be used as binders all other polymers are used, but the above products play a role by far the greatest role in this sector.

The binders mentioned exercise the migration of the water-insoluble Dye has a negative influence, i.e. the dye migration is through increases the binder. The increased migration through the binder can occur in the case of the invention Use of high molecular weight polyethylene glycols as migration inhibitors the additional use of common aminoplasts can be reduced.

According to the invention, therefore, the coloring with pigment dyes is carried out at the same time made a treatment with aminoplasts.

By using the aminoplasts, the effect of the migration inhibitor is increased positively influenced and thereby an optimal prevention of migration achieved, which results in a level dyeing even under the most unfavorable drying conditions expresses.

According to the subject matter of the present patent application are therefore in the dye and finishing liquor in addition to the pigment, the binder and the migration inhibitor used according to the invention is an aminoplast and a corresponding one Curing catalyst included. The most varied of aminoplasts can be used according to the invention Crosslinking agent or

Self-crosslinking agents and mixtures thereof can be considered. It is about here to the methylol compounds of urea and cyclic, optionally substituted ilarnea compounds e.g. the di- or tetramethylol compounds of urea, ethylene urea, propylene urea, 5-hydroxypropylene urea, Dihydroethylene urea or acetylene diurea.

In addition, in the context of the present patent application, the Methylol compounds of aarbamates such as the methylol compounds of carbamif1säuremethyl-, -äthyl- and -propylextern or of carbamic acid hydroxyalkyl esters and the di-, Tri- and tetramylol compounds of biscarbamates of e.g. ethylene glycol and propylene glycol.

In addition, the aminoplasts are the polymethylol compounds of triazines, especially of melamine. The so-called triazone resins and uranium resins are also usable, but less suitable. Of course they can Methylol compounds as such or in the form of wholly or partly with alcohols with 1 to 3 carbon atoms etherified descendants, of course the hydroxyl groups in the nucleus can also be completely or partially etherified, can be applied. The methylol compounds of the cyclic urea derivatives are preferred, and their mixtures with those optionally etherified with lower alcohols Polymethylolmelaminen used. The amount of aminoplast depends on the desired wrinkle-free or. Wash-and-wear effect and is usually 10 to 100 g / l, preferably 15 to 70 g / l of the 100% product.

The known, potentially acidic hardeners are primarily used as catalysts for use. Such as magnesium chloride, aluminum sulfate, zinc chloride, zinc nitrate, Ammonium chloride, ammonium nitrate, ammonium phosphates and the salts of strong acids, in particular hydrochloric acid, with amines, preferably alkanolamines such as ethanolamine, Called diethanolamine and 2-methyl-2-aminopropanol. The salts mentioned can also together with organic acids such as tartaric acid, citric acid, oxalic acid or acetic acid can be used as catalysts. The amount of catalyst is not critical.

It is generally 10 to 40 gO by weight based on anhydrous Aminoplast.

In the method according to the invention for one-bath dyeing and finishing can easily add additional positive properties to the fabric at the same time be awarded.

Such is a combination with conventional plasticizers and hydrophilizing agents possible. Also a simultaneous hydrophobization with customary products, in particular based on silicone is quite possible, since the one used according to the invention Migration inhibitor the water-repellent effects are only negligibly negatively affected.

The high molecular weight polyethylene glycols are used together according to the invention used with aminoplasts for simultaneous dyeing and finishing. The procedure the common staining and finishing is carried out in the following way: In general, the necessary substances, i.e. the water-insoluble dye, the aminoplast and the catalyst necessary for curing, the binder and the Migration inhibitor used according to the invention and, if appropriate, the additional finishing agents still used in the specified amounts in water, the fabric soaked with the solution obtained, to a liquor pick-up of about 55 to 80 (depending on the fabric) pressed, then dried at a moderately elevated temperature and finally condensed at 125 to 17500 1/4 to 6 minutes.

Textiles are used for the process of simultaneous dyeing and finishing used, the at least partially cellulose fibers, be it natural or regenerated Cellulose fibers. Synthetic fibers in particular are used as mixed fibers, especially polyamide, polyester and polyacrylonitrile fibers in question. The synthetic one The proportion can definitely predominate.

According to the prior art, among other things, oxethylation products are used as Migration inhibitor used. Such products meet today's requirements no longer does justice to the uniformity of a color; because when using this Compounds the migration of the dye is reduced, but the migration problem is by no means solved.

So it was not to be found in the state of the art and was carried out by the same also not suggested that high molecular weight polyethylene glycols in excellent Way are suitable as migration inhibitors, as the compounds used so far deliver only a very satisfactory result despite a similar structure.

The technical progress of the subject matter of the invention is convincingly demonstrated in example 1. This progress lies in that practically no more migration of the dye occurs and at the same time, and this Advantage is very important, especially for commercial reasons, a noticeable one Improvement of the color yield is achieved. Another advantage is the Improved resistance to scrubbing should be mentioned, a property that allows long-term use of the dyed goods is significantly improved. The wrinkle-free effect is not impaired. Finally, it should be emphasized that when using the high molecular weight polyethylene glycols no significant impairment of the impregnation effects in the case of co-use water repellent occurs.

The subject matter of the present patent application is therefore a achieved a considerable enrichment of the state of the art, since this is the only way to achieve the Problem of migration when dyeing together with water-insoluble dyes and equipping can be considered solved.

The test results given in the following examples were determined by the following methods: 1. Wet migration The pad-moist sample is placed halfway between 2 glass plates and loaded with a weight of 1 kg.

The sample is then allowed to dry at room temperature and assessed on a scale from 1 to 5 as follows: Grade 1 = covered part very strong discolored, dye migrated almost evenly into the free part.

Grades 2 - 4 = covered part strongly to slightly discolored, dye wandered more or less heavily into the free part.

Grade 5 = covered part not or only slightly lighter than that free part.

2. Dry migration When drying under heating, migration occurs especially on the parts of the fabric that come into contact with metal parts, e.g. on the pin strips of a sample frame.

The evaluation is carried out as follows: Grade 1 = fabric at points of contact almost colorless, furthermore the coloring is very uneven.

Grades 2-4 = tissue at the points of contact low, moderate or good colored, coloring more or less uneven.

Grade 5 = fabric completely uniform and even at points of contact no matter colored.

3. Resistance to scrubbing The finished colored pattern takes 30 seconds long in a solution of 5 g / l Marseille soap and 2 g / l soda together with one medium-hard toothbrush introduced, then stretched over a board and with the toothbrush Rubbed back and forth 30 times (applied pressure 750 br).

Then it is rinsed with distilled water, dried and the brightening assessed at the friction point according to the following scale: 1 = extensive bleaching 2 = very strong lightening 3 = significant lightening 4 = noticeable to slight lightening 5 = no noticeable lightening 4. Dry wrinkle resistance The dry wrinkle angles are determined according to DII4 5 53890.

5. Water repellency and beading effect These two tests are carried out according to DIN 53888.

When specifying the molecular weights for the exposed polyethylene glycols are average values.

Example 1 a) A bleached cotton / polyester blend fabric (50:50 intimate mix; 130 g / m2) is padded with the following aqueous dye and finishing liquor: 80 g / l of a 50% strength aqueous dimethyloldihydroxyethylene urea solution, 50 g / l a mixture consisting of a 40, d0igen nonionic dispersion of a copolymer from butyl acrylate and butyl methacrylate and a 25% nonionic Polyethylene secondary emulsion (ratio 2: 1), 40 g / l of a 9% aqueous solution of polyethylene glycol with a molecular weight (MW) of approx. 300,000, 8 g / l zinc chloride and 5 g / l of a blue pigment dye (Color Index 74160).

The liquor pick-up is 65%. The drying took place on frames with metal pin bar at 1000C and the condensation for 5 minutes at 1500C.

The results obtained with this equipment are shown below Table, the following values are also given for comparison: b) Equipment as above, but with 10 g / l of a 50% strength aqueous solution of an ethoxylated fatty alcohol (MW approx. 6000; cloud point 4000) according to the prior art instead of polyethylene glycol as a migration inhibitor.

c) Equipment as above, with comparatively 10 g / l of a 5Noigen aqueous solution of polyethylene glycol (MW approx. 6000) instead of polyethylene glycol with MG approx. 300,000 was used.

d) Equipment as above, but without a migration inhibitor.

a) (inventive b) (state of c) (ver d) (according to) technology) same) same) wet migration 4-5 1-2 2 1 dry migration 5 2 2-3 1-2 fastness to scrubbing 4 3 3-4 3 Yield of dye very good moderate moderate - moderately good dry crease - 1300 1310 1300 1290 angle Around the impregnation influence by the migration inhibitor to check, experiments a) and b) were repeated, using the treatment solution additionally contained the following ingredients: 40 g / l of the silicone emulsion according to the example 5 of US Pat. No. 3,748,275 and 15 g / l of the above aqueous catalyst emulsion (contains 1 mole of versatic acid and 1 mole of lauric acid per g atom of zirconium; as an emulsifier 2 C / Octadecyloxymethylpyridinium chloride).

The water-repellent effects obtained are listed below: a 1) (invention b 1) (prior art) water absorption in Vo 8.3 14.2 beading effect 4-3-3 2-1 Example 2 A cotton / polyester blend fabric (33:67; 150 g / m2) is like indicated in Example 1, treated, The treatment liquor shows the following composition: 90 g / l of the above aqueous solution of a mixture of aminoplasts (dimethylolethylene urea and pentamethylolmelamine etherified with methanol in a weight ratio of 2: 1) 40 g / l of a 30% aqueous emulsion of a copolymer of 2-ethylhexyl acrylate and acrylonitrile, 60 g / l of a 15% aqueous solution of polyethylene glycol (MG approx. 150,000) 4.5 g / l 2-methyl-2-aminopropanol hydrochloride (in the form of a 35% aqueous solution) and 6 g / l of an orange pigment (C.I. 21115).

The assessment of the migration gives the following picture, with the comparative equipment according to the information in example 1) have been carried out: Equipment a) b) d) (inventive (state of the (comparison) according to) technology) wet migration 4 2 1-2 dry 5 2 1-2 migration The coloration according to process a) according to the invention is clear deeper than the comparison equipment, i.e. the result is a noticeably better one Dye yield.

The migration inhibitor can easily against 120 g / l of a 2 above aqueous solution of polyethylene glycol (MW approx. 70,000) are exchanged.

Example 3 The fabric given in Example 1 is used in that described there Way dyed and finished in the following liquor at the same time: 70 g / l of a 50 aqueous solution of dimethylol dihydroxyethylene urea, 15 g / l hexamethylol melamine Etherified with methanol (in the form of an own aqueous solution), 40 g / l of a 40% own aqueous dispersion of a copolymer of butyl acrylate, acrylonitrile, vinyl chloride and N-methylolacrylamide (ratio 6: 2: 1.5: 0.5), 35 g / l of a 5% strength aqueous Solution of polyethylene glycol (MW approx. 1 million), 10 g / l magnesium chloride (in the form of the hexahydrate) and 3 g of a green pigment (C.I. 74260).

With this finish, there is practically no migration of the dye on. The crease resistance can be described as quite normal. The handle the finished goods are pleasantly soft.

Example 4 A bleached cotton / polyamide 80:20 mixed batiste (90 gS / m2) is impregnated with the following liquor: 40 g / l of a 50% aqueous dimethylolethylene urea solution, 50 g / l binder (see Example 1), 40 g / l of a doigen aqueous solution of polyethylene glycol (MW approx. 2 million), 4 g of zinc chloride and 10 g / l of a blue disperse dye of the formula After the fabric has been pressed to a liquor pick-up of 62%, it is dried at 11,000 and then condensed at 15,500 for 4 minutes.

In addition to very good migration prevention, the Polyethylene glycol has a round, pleasantly full handle. It also occurs at the same time Hydrophobization with customary silicone emulsions does not cause any significant deterioration the impregnation values. The anti-crease effects are also in this case in the usual, known frame.

Equally good results are obtained if dimethylolethyleneurea is used instead the same amount of Dimethylolpropylenurea used and a catalyst Mixture of 10 g / l magnesium chloride hexahydrate and 1 g / l glycolic acid used will.

EXAMPLE 5 A mercerized, bleached cotton poplin (126 g / m2) is dyed in a single bath and finished according to the following procedure: The fabric is 60% strength with a liquor containing 60 g / l hexamethylolmelamine tetramethyl ether, 16 g / l zinc chloride, 1 g / l acetic acid 40 g / l of a 287% aqueous dispersion of a copolymer of 89 parts of butyl acrylate, 5 parts of butanediol diacrylate and 6 parts of ethyl acrylate (as emulsifier 4, based on the copolymer, a nonylphenol polyglycol ether ethoxylated with 9 ethylene oxide) show 50 g / l aqueous solution of polyethylene glycol (MW approx. 500,000) and 12 g / l of a green disperse dye of the formula contains, soaked, squeezed off to a liquor pick-up of 68 (fo, dried and condensed in a known manner at 1500C for 4 minutes.

The fabric finished in this way shows a level color loss, i.e. none Migration. Particularly noteworthy is the high resistance to scrubbing of the equipment. The dye yield is excellent. The equipment also shows a full, round handle.

Example 6 Example 1) is repeated, but instead of the aminoplasts used there, the same amounts of the following compounds are used: Migration of the dye is prevented to an excellent extent in all cases. The resistance to scrubbing is also excellent for all equipment. Finishes 1) and 2) also show a particularly pleasant and soft grip.

Claims (13)

Claims 1. Use of polyethylene glycols with molecular weights of 30,000 up to 5 million as iration inhibitors in dyeing and simultaneous finishing of at least partially cellulose-containing textiles with water-insoluble Dyes in the presence of aminoplasts and curing catalysts in known Way. 2. Use according to claim 1, characterized in that 1 up to 30 t / l polyethylene; lycoles can be used. 3. Use according to claim 1 and 2, characterized in that that 3 to 20 g / l polyethylene glycols are used. 4. Use according to claim 1 to 3, characterized in that that polyethylene glycols with a molecular weight of 50,000 to 2 million are used. 5. Use according to claim 1 to 4, characterized in that that as aminoplasts, the methylol compounds of ureas, as well as their mixtures with the polymethylolmelamines, optionally etherified with lower alcohols be used. 6. Use according to claim 1 to 5, characterized in that that 10 to 100 g / l aminoplasts, calculated as anhydrous product, are used. 7. Method of dyeing and simultaneous finishing of at least some textiles containing cellulose with water-insoluble dyes in Presence of migration inhibitors, aminoplasts, H; irtunÓ catalysts and binders in the usual way by padding, drying and condensing, characterized in that that the Treatment liquors as a migration inhibitor 1 to 30 g / l Polyethylene glycols with a molecular weight of 30,000 to 5 million and the aminoplasts in amounts of 10 to 100 g / l, calculated as anhydrous product, can be added. 8. The method according to claim 7, characterized in that 3 up to 20 g / l polyethylene glycols can be added. 9. The method according to claim 7 and 8, characterized in that that polyethylene glycols with a molecular weight of 50,000 to 2 million were added will. 10. The method according to claim 7 to 9, characterized in that that methylol compounds optionally etherified with lower alcohols as aminoplasts of urea, cyclic ureas, carbamates, melamine and / or their mixtures can be added. 11. The method according to claim 10, characterized in that as aminoplasts, the methylol compounds of dihydroxyethylene urea, ethylene urea, Propylene urea, hydroxypropylene urea and acetylene diurea and mixtures thereof with polymethylolmelamines etherified with lower alcohols if necessary will. 12. The method according to claim 7 to 11, characterized in that that 15 to 70 g / l aminoplasts, calculated as anhydrous product, are added. 13. The method according to claim 7 to 12, characterized in that that other conventional finishing agents are added.