EP0703305A1 - Process for the production of aminated regenerated cellulose - Google Patents

Abstract

The prodn. of aminated regenerated cellulose fibres (I) comprises making a soln. of cellulose and a protein with a mol. wt. of more than 50000 or a natural prod. contg. such a protein (II) and spinning fibres from this soln. Also claimed are (i) textile fibre material consisting of (I); and (ii) a process for dyeing and printing such textiles with anionic dyes, using a dye soln. contg. no additional electrolyte salts, at a pH of 4-6 for direct and acid dyes and 6-8.5 for reactive dyes.

Description

In their dyeing behavior, viscose fibers are essentially the same as those of cotton fibers. In the current state of the art, alkaline dispensing agents and electrolytes are required for dyeing cellulosic natural or regenerated fibers in order to achieve satisfactory fixing results with reactive dyes. For ecologically improved dyeing processes, however, it is precisely these necessary additives which are unacceptable environmental impacts. For the future, regenerated fibers based on cellulose will therefore be of increasing importance. They have previously been converted into highly dye-affine, i.e. Salt and alkali-free dyeable modifications have been transferred. The chemical behavior of fibers modified in this way is similar to that of animal fibers, such as wool or silk, and can be dyed under neutral conditions with anionic dyes, without further salt or alkali additives.

Modifications of viscose have already been described in the literature. DE-A-1 948 487, for example, describes a process for producing viscose fibers with changed dyeing properties. The production is extremely complex and uneconomical. In addition, polyaminamides are used, which significantly disrupt the native character of the fiber. This is expressed, for example, by the use of disperse dyes in the later dyeing.

DE-A-1 469 062 also deals with "aminalized fibers". The additives are aminoethyl and diethylaminoethyl celluloses in high concentration, coloring is done exclusively with acid dyes.

The object of the present invention was to provide modified viscose fibers in order to dye textiles from such fibers with low salt and alkali with anionic dyes and to obtain a fabric with a soft feel.

It has been found that by using proteins as an additive to the viscose mass or to the cellulose prior to alkalizing, a viscose fiber can be produced which, surprisingly, is significantly more affinity when dyed with anionic dyes and which has the desired properties compared to conventional viscose fibers, for example due to a soft feel clearly differentiates.

The present invention relates to a process for the production of regenerated cellulose regenerated fibers, characterized in that a solution of cellulose and a protein with a molecular weight of greater than 50,000 or a natural product containing such a protein is prepared and fibers are spun from this solution.

In a preferred embodiment, the procedure is such that a) cellulose and a protein with a molecular weight greater than 50,000 or a natural product which contains such a protein are mixed and the mixture is subjected to alkaline digestion and the resulting alkaline digested mixture is reacted with carbon disulphide or b) a protein with a molecular weight greater than 50,000 or a natural product which contains such a protein, dissolves in sodium hydroxide solution and adds it to a spinning viscose, and transfers the viscose spinning solution obtained according to a) or b) into an acidic spinning bath and spins it into fibers.

The reaction with carbon disulphide expediently takes place at temperatures of 15 to 30 ° C. Subsequent spinning in an acidic spin bath gives the aminated cellulose fibers according to the invention.

It is also possible to produce the fibers according to the invention by other customary processes known to those skilled in the art for producing cellulosic fibers from solution, such as, for example, the cupro process, the lyocell process and the process using low-substituted cellulose ethers. The cellulose and the protein are dissolved in a suitable organic solvent, for example N-methylmorpholine-N-oxide / water, reacted with one another and spun directly from the solution into fibers.

After spinning in an acidic spinning bath, fibers are obtained which can be dyed according to the invention using low-electrolyte or completely electrolyte-free and alkali-free or alkali-free dyeing liquors (including printing pastes and ink-jet liquids). Low-electrolyte dyeing liquors are understood to mean those with an electrolyte content of less than 15 g / l and low-alkali dyeing liquors to those with a pH of at most 8.5.

The proteins and protein-containing natural products used for the process according to the invention occur in nature, for example, as keratins, collagen-containing natural products and albumins. Examples of preferably used keratins are body hair, hooves, horns, claws and nails from mammals, bird feathers, spider threads from insects, tortoiseshell and fish scales. Examples of preferred natural products containing collagen are dermis, leather, cartilage, connective tissue, tendons, ligaments of mammals, in particular gelatin, glutin and bone glue. Egg albumin or eggs as such are particularly suitable as albumin.

The protein-containing natural products used for the method according to the invention can also contain other accompanying components, for example meat, meat meal, fish, fish meal or processing products thereof can also be used.

The proteins are denatured in the course of the dissolving process. In addition to the animal proteins mentioned, synthetic proteins with a molecular weight greater than 50,000 can also be used.

The textile-modified fiber material that is used in the dyeing process according to the invention can be present in all processing states, such as yarn, flake, sliver and piece goods (fabric).

In the amination of the regenerated cellulose according to the invention, there is probably no chemical reaction between the cellulose and the alkaline-digested or dissolved protein, but the two components adhere so strongly to one another in the fiber as a result of Van der Waals interactions that the protein cannot be washed out .

The dyeing of the aminated textile fiber materials according to the invention is carried out analogously to known dyeing methods and printing processes for dyeing or printing fiber materials with water-soluble textile dyes and using the temperature ranges and customary amounts of dye known to be used for this, but with the exception that for the dye baths, padding liquors, printing pastes or ink Jet formulations a quantitative addition of alkaline compounds, as they are usually used for fixing fiber-reactive dyes, is not necessary and furthermore, the usual additions of electrolyte salts can be dispensed with. The dyeing of the modified viscose according to the invention takes place between pH 4 and pH 8.5, depending on the type of dye. When using commercial textile dyes, salt contents of 0.01 to 0.5% by weight, based on the dyeing liquor, are normally present. Without the amination of the cellulose fibers according to the invention, however, this salt content would be too low by a factor of 50 to 1000 for a successful dyeing process.

The incorporation of the alkaline digested or dissolved protein into the viscose spinning mass is advantageously carried out without emulsifiers. The protein is added in an amount of 1 to 20% by weight, preferably 1 to 12% by weight, based on the cellulose content of the dope, before the precipitation and shaping.

The viscose is deformed using customary methods, such as with spinnerets, a subsequent precipitation bath and, if necessary, further post-treatment baths.

The fibers obtained by the described methods can be dyed after processing into fabrics and knitted fabrics, using a wide variety of processes, such as exhaust, padding and modern printing processes - and this includes ink-jet processes - without the use of salt or alkali.

The present invention also relates to a process for dyeing and printing cellulose fiber-containing textiles with anionic dyes, characterized in that the dyeing is carried out with a dye solution which is free of additional electrolyte salts, at a pH between 4 and 6 in the case of direct - and acid dyes and at a pH between 6 and 8.5 in the case of reactive dyes and using a cellulose regenerated fiber material aminated according to the invention.

The dyeing process can be, for example, the various exhaust 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 by padding-cold dwelling or padding-hot steam fixing . Conventional printing techniques, including ink jet printing and transfer printing, can be considered as printing processes.

The dyes used to dye the modified cellulose are generally anionic in nature. In addition to the so-called acid or direct dyes, the fiber-reactive textile dyes are those which can react with hydroxyl groups, for example of cellulose, or amino and thiol groups, for example of wool and silk, of synthetic polymers, such as polyamides, or also the celluloses aminated according to the invention, and one covalent bond are particularly suitable. The sulfatoethylsulfonyl, vinylsulfonyl, chlorotriazinyl and fluorotriazinyl group and combinations of these reactive groups may be mentioned in particular as fiber-reactive components on the textile dyes.

Suitable reactive dyes for dyeing or printing cellulose fibers modified according to the invention are all water-soluble, preferably anionic dyes, which preferably have one or more sulfo and / or carboxy groups and which contain fiber-reactive groups. Suitable dyes can be the class of azo development dyes, direct dyes, vat dyes and acid dyes, copper complex, cobalt complex and chromium complex azo dyes, copper and nickel phthalocyanine dyes, anthraquinone, copper formazane, azomethine, nitroaryl, dioxazine -, Triphendioxazin-, Phenazin- and stilbene dyes belong. Such dyes have been described in numerous publications, for example in EP-A-0 513 656, and are well known to those skilled in the art.

Examples of suitable acid or direct dyes for dyeing or printing cellulose fibers modified according to the invention are CI Acid Black 27 (CI No. 26 310), CI Acid Black 35 (CI No. 26 320), CI Acid Blue 113 (CI No. 26 360) , CI Direct Orange 49 (CI No. 29 050), CI Direct Orange 69 (CI No. 29 055), CI Direct Yellow 34 (CI No. 29 060), CI Direct Red 79 (CI No. 29 065), CI Direct Yellow 67 (CI No. 29 080), CI Direct Brown 126 (CI No. 29085), CI Direct Red 84 (CI No. 35 760), CI Direct Red 80 (CI No. 35 780), CI Direct Red 194 (CI No. 35 785), CI Direct Red 81 (CI No. 28 160), CI Direct Red 32 (CI No. 35 790), CI Direct Blue 162 (CI No. 35 770), CI Direct Blue 159 (CI No. 35 775), CI Direct Black 162: 1 and CI Direct Violet 9 (CI No. 27 885) suitable.

Unless stated otherwise, the parts listed in the examples below are parts by weight, percentages mean percentages by weight.

example 1

über eine Zeit von 30 min zu. Nach einer Nachlaufzeit von 5 min wird die farblose Restflotte abgelassen und das Material nach gängigen Methoden ausgewaschen und getrocknet. Man erhält eine farbstarke tiefrote Färbung mit sehr guten Gebrauchsechtheiten.An alkaline solution of sheep's wool is stirred into an industrial spinning viscose with a cellulose content of 8.9%, an alkali content of 5% and a viscosity of 38 falling seconds at 30 ° C. The procedure is as follows:
6 parts of wool are dissolved in a solution containing 10 parts of sodium hydroxide and 90 parts of water. 59 parts of this solution are mixed with 1000 parts of a commercial spin viscose containing 89 parts of cellulose. After degassing, the spinning mass is spun into fibers using a customary viscose spinning process in a sulfuric acid, sodium and zinc sulfate bath, stretched in acidic baths, cut, washed, prepared and dried.
10 parts of these dry viscose fibers are then mixed with 100 parts of water in a dyeing apparatus. The mixture is heated to 60 ° C. and a total of 0.1 part of a 50% electrolyte-containing (predominantly sodium-containing) dye powder of the formula known from DE-A-1 943 904 is metered in.

over a period of 30 min. After a follow-up time of 5 min the remaining colorless liquor is drained and the material is washed and dried using standard methods. A deep red color with very good fastness properties is obtained.

Example 2

gelöst enthält, behandelt. Man färbt die Fasermischung 30 Minuten bei 60°C. Die Weiterbehandlung der so erzeugten Färbung erfolgt durch Spülen und Seifen in der üblichen Weise. Man erhält eine tiefblaue Färbung mit den nach dem Stand der Technik üblichen sehr guten Gebrauchsechteiten.10 parts of the viscose fibers modified according to Example 1 are transferred to a dyeing machine and treated in a liquor ratio of 1:10 with an aqueous liquor which, based on the fabric weight of the dry fabric, 0.1 parts of a reactive dye of the formula known from DE -A-24 12 964

contains dissolved, treated. The fiber mixture is dyed at 60 ° C. for 30 minutes. The dyeing thus produced is further treated by rinsing and soaping in the customary manner. A deep blue color is obtained with the very good usage fastness customary in the prior art.

Example 3

bekannt aus EP-A-0 158 233, Beispiel 1, und 3 Teile eines handelsüblichen nichtionogenen Benetzungsmittels gelöst enthält, mittels eines Foulards mit einer Flottenaufnahme von 80 %, bezogen auf das Gewicht des Gewebes, bei 25°C auf das Gewebe aufgebracht. Das mit der Farbstofflösung geklotzte Gewebe wird auf eine Docke aufgewickelt, in eine Plastikfolie gewickelt und während 4 Stunden bei 40 bis 50°C liegen gelassen und danach mit kaltem und heißem Wasser, das gegebenenfalls ein handelsübliches Tensid enthalten kann, und gegebenenfalls anschließend nochmals mit kaltem Wasser gespült und getrocknet. Es wird eine farbstarke, gleichmäßig gefärbte gelbe Färbung erhalten, die gute Allgemeinechtheiten, insbesondere gute Reib- und Lichtechtheiten, besitzt.A spunbond viscose produced as described in Example 1 is spun into fibers after degassing by a customary viscose spinning process in a bath containing sulfuric acid, sodium and zinc sulfate, stretched in acid baths, cut, washed, prepared and dried. After weaving, a textile viscose fabric is obtained which can be further processed directly in a dyeing process using the block method. For this purpose, an aqueous dye solution containing 20 parts of the in 1000 parts by volume Dye of the formula

known from EP-A-0 158 233, Example 1, and 3 parts of a commercially available nonionic wetting agent dissolved, by means of a pad 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 for 4 hours at 40 to 50 ° C and then with cold and hot water, which may or may not contain a commercially available surfactant, and then optionally again with cold water Rinsed water and dried. A strong, uniformly colored yellow coloration is obtained which has good general fastness properties, in particular good fastness to rubbing and light.

Example 4

bekannt aus der EP-A-00 61 151, Beispiel 4, in handelsüblicher Form und Beschaffenheit enthält. Man färbt die Faser mit dieser Flotte 30 min bei 60°C. Die Weiterbehandlung der so erzeugten Färbung erfolgt durch Spülen und Seifen in üblicher Weise. Es resultiert eine lebhafte Orangefärbung mit den für Reaktivfarbstoffe üblichen, guten Echtheiten.An alkaline solution of a commercially available gelatin is stirred into a commercially available spinning viscose with a cellulose content of 9%, an alkali content of 5.5% and a viscosity of 40 falling balls at 30 ° C. The procedure is as follows:
6 parts of gelatin are dissolved in a solution containing 10 parts of sodium hydroxide and 90 parts of water. 59 parts of this solution are mixed with 1000 parts of a commercial spin viscose containing 89 parts of cellulose. After degassing, spinning, stretching, cutting, washing and drying, a fiber is obtained which is produced using a conventional drawing-out process can be colored. For this, 20 parts of the pretreated viscose fiber are treated in a dyeing machine with 200 parts of an aqueous liquor which, based on the weight of the dry goods, contains 1.5% of the reactive dye of the formula

known from EP-A-00 61 151, Example 4, in a commercially available form and composition. The fiber is dyed with this liquor at 60 ° C. for 30 minutes. The dyeing thus produced is further processed by rinsing and soaping in the customary manner. The result is a lively orange color with the good fastness properties customary for reactive dyes.

Example 5

bekannt aus DE-A-28 40 380, Beispiel 1, enthält. Den pH-Wert stellt man mit Na-Bicarbonat auf 8. Man heizt auf 60°C auf, wobei die Flotte im Wechsel von innen nach außen und von außen nach innen gepumpt wird. Nach 60 min bei dieser Temperatur läßt man die Flotte ab, spült und wäscht nach den üblichen Konditionen die erhaltene Färbung nach. Man erhält eine egal gelb gefärbte Faser mit den allgemein guten Echtheiten für Reaktivfarbstoffe.An alkaline solution of horsehair is stirred into an industrial spinning viscose with a cellulose content of 8.8%, an alkali content of 5% and a viscosity of 41 falling balls at 30 ° C. For this purpose, 8 parts of horsehair are dissolved in a solution containing 11 parts of sodium hydroxide and 100 parts of water. 65 parts of this solution are mixed with 1000 parts of a commercial spinning viscose containing 89 parts of cellulose. After further processing according to the process steps customary for spinning viscose, a fiber of modified viscose is obtained, which can be reactively dyed in a pull-out process without salt and at a pH of 8. For this purpose, 30 parts of viscose fiber are wound on a cross-wound bobbin and the yarn is treated in a yarn dyeing apparatus, the 450 parts (based on the weight of the goods) of a liquor, the 0.6 parts, based on the initial weight of the goods, of an electrolyte-containing dye (predominantly containing sodium chloride) general formula,

known from DE-A-28 40 380, Example 1 contains. The pH is adjusted to 8 with sodium bicarbonate. The mixture is heated to 60 ° C., the liquor being pumped alternately from the inside to the outside and from the outside to the inside. After 60 minutes at this temperature, the liquor is drained off, rinsed and washed according to the usual conditions, the dyeing obtained. An irrespective yellow colored fiber with generally good fastness properties for reactive dyes is obtained.

Example 6

enthält. Den pH-Wert der Flotte stellt man zuvor mit Essigsäure auf 4,5. Man färbt die Faser mit dieser Flotte 30 min bei 80°C. Die Weiterbehandlung der so erzeugten Färbung erfolgt durch Spülen und Seifen in üblicher Weise. Es resultiert eine kräftige Blaufärbung mit Echtheiten, die denen konventioneller Direktfärbungen weit überlegen ist. Dies betrifft vor allem die Waschechtheiten.An alkaline solution of ground horn shavings is stirred into an industrial spinning viscose with a cellulose content of 8.9%, an alkali content of 5% and a viscosity of 38 falling ball seconds at 30 ° C. The procedure is as follows:
7 parts of ground horn shavings are dissolved in a solution containing 11 parts of sodium hydroxide and 100 parts of water. 55 parts of this solution are mixed with 1000 parts of a commercial spin viscose containing 90 parts of cellulose.
After degassing, spinning, stretching, cutting, washing and drying, a fiber is obtained which can be dyed at pH 4.5 using a conventional pull-out process.
To this end, 20 parts of the pretreated viscose fiber are negotiated in a dyeing machine with 200 parts of an aqueous liquor which, based on the weight of the dry goods, 2% of the direct dye of the formula (CI Direct Blue 108, CI 51320)

contains. The pH of the liquor is previously adjusted to 4.5 with acetic acid. The fiber is dyed with this liquor at 80 ° C. for 30 minutes. The dyeing thus produced is further processed by rinsing and soaping in the customary manner. The result is a strong blue dyeing with fastness properties that are far superior to conventional direct dyeings. This concerns above all the wash fastness.

Example 7

und 3 Teile eines handelsüblichen nichtionogenen Benetzungsmittels gelöst enthält, mittels eine Foulards mit einer Flottenaufnahme von 80 %, bezogen auf das Gewicht des Gewebes, bei 25°C auf das Gewebe aufgebracht. Die Farbstofflösung wurde zuvor mit Essigsäure auf einen pH-Wert von 5 gestellt. Das mit der Farbstofflösung geklotzte Gewebe wird anschließend 2 Minuten gedämpft. Die Weiterbehandlung der so erzeugten Färbung erfolgt durch Spülen und Seifen in üblicher Weise. Es resultiert eine kräftige Türkisfärbung mit sehr guten Allgemeinechtheiten.An alkaline solution of pigskin is stirred into an industrial spinning viscose with a cellulose content of 9%, an alkali content of 6% and a viscosity of 42 falling balls at 30 ° C. The procedure is as follows:
6 parts of pig skin are dissolved in a solution containing 10 parts of sodium hydroxide and 90 parts of water. 55 parts of this solution are mixed with 1000 parts of a commercial spin viscose containing 90 parts of cellulose. After the usual process for fiber production and weaving, a textile viscose fabric is obtained which can be further processed directly in a dyeing process using the block process. For this purpose, an aqueous dye solution containing 20 parts of the direct dye of the formula (CI Direct Blue 199) in 1000 parts by volume

and 3 parts of a commercially available nonionic wetting agent contains, by means of a foulards with a liquor absorption of 80%, based on the weight of the fabric, applied to the fabric at 25 ° C. The dye solution was previously adjusted to a pH of 5 with acetic acid. The fabric padded with the dye solution is then steamed for 2 minutes. The dyeing thus produced is further processed by rinsing and soaping in the customary manner. The result is a strong turquoise color with very good general fastness properties.

Further examples:

The procedure is as described in Examples 4, 5, 6 or 7 and the modified viscose fiber is dyed in accordance with the instructions in Example 6 using the dyes listed below and the same results are obtained:

Claims (11)

Process for the production of aminated cellulose regenerated fibers, characterized in that a solution of cellulose and a protein with a molecular weight of greater than 50,000 or a natural product containing such a protein is produced and fibers are spun from this solution. A method according to claim 1, characterized in that a) cellulose and a protein with a molecular weight greater than 50,000 or a natural product which contains such a protein, mixes and breaks the mixture up alkaline and converts the resulting alkaline digested mixture with carbon disulphide or b) a protein with a molecular weight greater than 50,000 or a natural product which contains such a protein, dissolves in sodium hydroxide solution and adds it to a spin viscose, and the viscose spinning solution obtained according to a) or b) is transferred into an acidic spinning bath and spun into fibers. Process according to Claim 1, characterized in that cellulose and said protein are dissolved in a suitable organic solvent and fibers are spun directly from the solution. Method according to at least one of claims 1 to 3, characterized in that the protein is a keratin, a collagen-containing natural product or an albumin. Process according to at least one of Claims 1 to 4, characterized in that body hair, skins, hooves, horns, claws and nails from mammals, bird feathers, fish scales, spider threads from insects or gelatin are used as the protein. Process according to at least one of Claims 1 to 5, characterized in that the protein is used in an amount of 1 to 20% by weight, preferably 1 to 12% by weight, based on the cellulose content of the spinning mass. Textile fiber material consisting of aminated cellulose regenerate fibers according to one or more of Claims 1 to 6. Process for dyeing and printing cellulose fiber-containing textiles with anionic dyes, characterized in that the dyeing is carried out with a dye solution which is free of additional electrolyte salts, at a pH between 4 and 6 in the case of direct and acid dyes and at a pH -Value between 6 and 8.5 in the case of reactive dyes and using a textile fiber material according to claim 7. A method according to claim 8, characterized in that the electrolyte content of the dye solution is below 15 g / l. A method according to claim 8 or 9, characterized in that the dyes are reactive dyes. A method according to claim 8 or 9, characterized in that the dyes are acid or direct dyes.