Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/58—Material containing hydroxyl groups
  • D06P3/60—Natural or regenerated cellulose
  • D06P3/66—Natural or regenerated cellulose using reactive dyes
  • D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
  • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
  • D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/58—Material containing hydroxyl groups
  • D06P3/60—Natural or regenerated cellulose
  • D06P3/66—Natural or regenerated cellulose using reactive dyes
  • D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/82—Textiles which contain different kinds of fibres
  • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
  • D06P3/8223—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups
  • D06P3/8228—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using one kind of dye
  • D06P3/8233—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using one kind of dye using dispersed dyes

Definitions

• electrolyte salts such as sodium chloride and sodium sulfate
• one alkaline agent such as sodium carbonate, sodium hydroxide or water glass
• CH-A-747 954 and CH-A-574 536 describe reaction products of polyethyleneimine with dicyandiamide or cyanamide and their fixation.
• DE-A-2 214 966 also pretreates with polyimines and polyamines, but immediately afterwards dyed with fiber-reactive dyes. In the case of pull-out dyeing, undesirable flocculation occurs, since the polyamines and polyimines can be detached from the fiber and then react and flocculate with the dyes.
• the number of primary or secondary amino groups in the polymer of formula (I) is preferably 10 to 500.
• the distance between the amino groups in the polymer can be varied within a wide range by intervening alkylene or alkyleneoxy groups.
• Preferred polymers of the formula (I) are polyethyleneimines with a molecular weight of 500 to 2000 and polypropyleneimines with a molecular weight of 500 to 1000.
• Preferred bifunctional crosslinking agents of the formula (II) are glyoxal, oxalic acid, malonic acid, succinic acid, diethyl oxalate, diethyl malonate and diethyl succinate.
• Dialdehydes can also be present as acetals or hemiacetals.
• Fiber materials are understood to mean natural and synthetic fiber materials which contain hydroxyl and / or carbonamide groups, such as silk, wool and other animal hair, as well as synthetic polyamide fiber materials and polyurethane fiber materials, for example polyamide-4, polyamide-6 and polyamide-11, and in particular fiber materials which Base bodies of ⁇ , ⁇ -glucose contain, such as cellulose fiber materials, for example cotton, hemp, jute and linen, and their regenerated derivatives, such as viscose silk and rayon, or mixtures of such fiber materials.
• the compounds of formulas (I) and (II) and the dye are dissolved in water, optionally the aqueous solution is a small amount of alkali, electrolyte or other conventional additives, such as. B. wetting agents (surfactants) added.
• the concentration of the polymers of the formula (I) in the aqueous treatment solution is advantageously 1 to 30% by weight, preferably 2 to 20% by weight, and that of the compounds of the formula (II) 0.5 to 20% by weight , preferably 1 to 10% by weight.
• the solution can be cooled and / or made alkaline. This is conveniently done with Na2CO3 or NaOH.
• the concentration of the alkali in the treatment solution is in the range from 0 to 20% by weight, preferably 0 to 5% by weight, and depends on the stability of the solution to be achieved. The lower the content of compounds of formula (I) and (II) in the solution, the more stable the mixtures are even without additives.
• the treatment solution and the dye solution are expediently brought into contact with the fiber material at temperatures between 10 and 100 ° C., preferably between 20 and 50 ° C.
• the fiber material which is both modified according to the invention and used in the modified form in the dyeing process, can be in all processing states, such as yarn, flake, sliver and piece goods (fabric), and also in a mixture with other fiber materials, such as in form of cotton / polyester fiber materials and in the form of blended fabrics with other fiber materials.
• the fiber material is impregnated with an alkaline aqueous solution by introducing the fiber material into this solution or by padding (padding), the impregnated material is then squeezed off by excess liquor, so that the absorption of this aqueous, alkaline solution is between 50 and 120% by weight .-%, preferably between 70 and 100 wt .-%, based on the fiber material.
• the impregnation (by padding, splashing or treatment in the solution itself) takes place at a temperature between 10 and 60 ° C., preferably at a temperature between 15 and 30 ° C.
• a liquid absorption of preferably between 10 and 50% by weight is selected.
• the impregnated material can be dried, a temperature of between 20 and 100 ° C., preferably between 30 and 50 ° C., being selected for the drying. As a rule, drying takes place by treatment with hot air for 0.5 to 3 minutes.
• the fiber material can also be processed wet immediately after the reaction with the compounds of the formulas (I) and (II).
• the customary aftertreatment of the modified fiber material is carried out by rinsing with cold and hot water and, if appropriate, by treatment in an aqueous bath containing a small amount of a surfactant to remove only superficially adhering compounds from the fiber material and possibly subsequent drying.
• a neutral-reacting fiber material should be used in the dyeing process if possible.
• the dyeing of such modified fiber materials according to the invention is carried out analogously to the known dyeing methods and printing processes for dyeing or printing fiber materials with water-soluble textile dyes, such as anionic dyes, in particular fiber-reactive dyes, and using the temperature ranges and customary amounts of dye known for this purpose, but with the exception according to the invention that for the dyebaths, padding liquors and printing pastes of the dyeing process according to the invention, an addition of alkaline compounds, as are usually used for fixing fiber-reactive dyes, such as sodium carbonate, potassium carbonate, sodium hydroxide solution and water glass, can be excluded to a large extent or even completely, and further the usual addition of electrolyte salts, which in particular should increase the migration of the dye on the fiber, not or only to a small extent, for example up to a maximum of 10 g per liter of dye bath or dye liquor is required.
• the dyeing process according to the invention is accordingly carried out within a pH range between 4 and 8, preferably between 4.5 and 7.
• Dyeing processes which can be used according to the invention are, for example, the various extraction processes, such as dyeing on the jigger and on the reel runner or dyeing from a long or short liquor, dyeing in jet dyeing machines, dyeing using the pad-cold-dwell method or after a block-hot steam fixing process. With the pull-out process you can work in the usual liquor ratio of 1: 3 to 1:20.
• the dyeing temperature can be between 30 and 90 ° C, preferably it is at a temperature below 60 ° C; As can be seen from the above-mentioned application of the pad-cold residence method according to the invention, dyeing is also advantageously possible at room temperature (10 to 30 ° C.)
• the use of the customary, often necessary dyeing aids such as surfactants (wetting agents), thiourea, thiodiethylene glycol, thickeners, leveling aids, auxiliaries which improve the solubility of dyes in the concentrated padding liquors, such as condensation products of formaldehyde and optionally alkyl-substituted Naphthalenesulfonic acids, and especially urea, can be omitted entirely or to a considerable extent.
• surfactants wetting agents
• thiourea thiodiethylene glycol
• thickeners thickeners
• leveling aids auxiliaries which improve the solubility of dyes in the concentrated padding liquors, such as condensation products of formaldehyde and optionally alkyl-substituted Naphthalenesulfonic acids, and especially urea
• the modified fiber material according to the invention can only be dyed using a purely aqueous dye solution, in which only extremely small amounts of electrolyte salts (such as sodium chloride and sodium sulfate), which are present as adjusting agents in the dye powders, are dissolved.
• electrolyte salts such as sodium chloride and sodium sulfate
• the present invention can also advantageously be used for single-bath dyeing processes for dyeing mixtures of cellulose and polyester fibers if, in addition, a disperse dye which is suitable for dyeing polyester fiber materials is used in the common dye bath with a reactive dye. Since many disperse dyes are sensitive to alkali, especially when using higher temperatures, they cannot be used in single-bath dyeing of cellulose / polyester mixed fiber materials, since the application of the high Temperatures in the alkali-containing bath when the polyester fiber is colored by the disperse dye leads to damage to the disperse dye.
• the present invention makes it possible to dye free of alkali, so that in the aqueous, alkali-free dyeing liquor, the reactive dye can first be fixed on the modified fiber material at a low temperature, for example at a dyeing temperature between 30 and 80 ° C., and then the polyester fiber the disperse dye is dyed in a conventional manner at temperatures above 100 ° C., for example between 110 and 140 ° C.
• All water-soluble, preferably anionic dyes which preferably have one or more sulfo and / or carboxy groups and which can optionally contain fiber-reactive groups, are suitable for the dyeing methods according to the invention.
• fiber-reactive dyes they can belong to the class of azo development dyes, direct dyes, vat dyes and acid dyes, which include, for example, azo dyes, copper complex, cobalt complex and chromium complex azo dyes, copper and nickel phthalocyanine dyes, anthraquinone and copper formazan -, Azomethine, nitroaryl, dioxazine, triphendioxazine, phenazine and stilbene dyes.
• azo development dyes direct dyes
• vat dyes and acid dyes which include, for example, azo dyes, copper complex, cobalt complex and chromium complex azo dyes, copper and nickel phthalocyanine dyes, anthraquinone and copper formazan -,
• the dyeings of the modified cellulose fiber materials obtainable in accordance with the invention require no further aftertreatment after removal from the dyebath or after completion of the fixation of the dye on the substrate, in particular no complex posttreatment process including washing.
• a fiber-reactive aftertreatment agent is advisable if the fiber material modified according to the invention has been dyed only in slight depths of shade or if a dye has been used which does not have satisfactory fiber reactivity. In these cases, there are still sufficient dye-reactive spots on the modified fiber, which, for example, can react with other dyes in rinsing baths contaminated with these dyes.
• This aftertreatment deactivates the still active areas of the fiber modified according to the invention, and the clear coloration originally desired is also obtained in a rinsing water used in a technical process and contaminated with dyes.
• a final boiling treatment of the colored substrate with a washing solution to improve the fastness properties is not necessary.
• the use of alkali can be dispensed with; the fixing times can also be drastically reduced. Furthermore, the process according to the invention for dyeing fiber materials modified according to the invention, in particular in the exhaust process, permits the single dyeing of polyester / cotton blended fabrics with reactive and disperse dyes without the disperse dye being damaged, precisely because alkali is not present in this single-bath dyeing process.
• the process according to the invention is advantageous from an ecological and economic point of view, since the impregnation and dyeing can be carried out in a simple manner and the polymers of the formula (I), if they are not present in the same solution with the compound of the formula (II), from the aqueous solution can be concentrated and regenerated.
• the present invention also relates to a fiber material modified by the method according to the invention and to a fiber material modified and dyed according to the invention.
• the invention relates to the use of such amino group-containing polymers and crosslinking agents as defined above for modifying fiber materials, in particular with the aim of being able to use them for dyeing with water-soluble, anionic dyes without or only with small amounts of electrolyte salts and alkaline agents.
• a strong, uniformly colored orange coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.
• a fabric made of mercerized and bleached cotton is mixed with a mixture consisting of a solution of 5% polyethyleneimine (MW: 2000), in which 4% Na2CO3 was previously added, and 4% glyoxal in water, using a commercially available inkjet printer which, according to a non-thermal process works (e.g. Piezzo), printed.
• the printing can take place over the entire fabric or even in patterns. In the case of a sample print, colorful patterns are created on a white background after coloring.
• the tissue thus obtained is dried at 50 ° C. in a circulating air cabinet.
• a cotton fabric modified in accordance with the above information is dyed in accordance with a block-cold-dyeing process.
• an aqueous dye solution containing 20 parts of 1000 parts by volume of a 50% electrolyte-containing dye powder of, for example, copper phthalocyanine dye of the formula known from German Patent No. 1,179,317 and contains 3 parts of a commercially available nonionic wetting agent dissolved, by means of a padder with a liquor absorption of 80%, based on the weight of the fabric, applied to the fabric at 25 ° C.
• the fabric padded with the dye solution is wound onto a dock, wrapped in a plastic film and left at 20 to 25 ° C for 16 hours and then with cold and hot water, which may or may not contain a commercially available wetting agent, and optionally again with cold water Washed water and dried.
• a strong, uniformly colored turquoise coloration is obtained which has good general fastness, in particular good fastness to rubbing and light.
• a cotton fabric modified as described in Example 4a) is printed with an aqueous printing paste containing 20 parts of the dye of the formula in 1000 parts (known from Example 3 of German Offenlegungsschrift No. 2 557 141) and contains 400 parts of an aqueous, 4% strength sodium alginate thickener.
• the printed fabric is first dried at about 60 to 80 ° C and then steamed for 5 minutes with superheated steam at 101 to 103 ° C.
• Example 10 parts of a cotton fabric modified according to the information in Example 1 a) is dissolved in 200 parts of an aqueous solution of 0.2 part of the dye of the formula (known from Color Index under CI No. 51320).
• the cotton fabric is dyed in this dye solution for 60 minutes at 60 ° C.
• the aftertreatment of the dyeing obtained is carried out in a customary manner, for example analogously to the instructions in Example 6.
• a strong blue dyeing is obtained which has very good fastness to use, in particular good fastness to washing.
• a strong, level, level red dyeing is obtained which, in its fastness properties, is equivalent in all points to the fastnesses of the dyeings obtainable by the processes of the prior art.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Dispersion Chemistry (AREA)
• Coloring (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Applications Claiming Priority (2)

Publications (3)

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• 1993
  • 1993-07-31 DE DE4325783A patent/DE4325783A1/de not_active Withdrawn
• 1994
  • 1994-07-25 EP EP94111572A patent/EP0636742B1/fr not_active Expired - Lifetime
  • 1994-07-25 DE DE59407370T patent/DE59407370D1/de not_active Expired - Fee Related
  • 1994-07-28 US US08/281,840 patent/US5512064A/en not_active Expired - Fee Related
  • 1994-07-29 JP JP6178905A patent/JPH07150477A/ja not_active Withdrawn

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